JPH04356504A - Method for lowering stereoregularity of syndiotactic polypropylene - Google Patents
Method for lowering stereoregularity of syndiotactic polypropyleneInfo
- Publication number
- JPH04356504A JPH04356504A JP13098591A JP13098591A JPH04356504A JP H04356504 A JPH04356504 A JP H04356504A JP 13098591 A JP13098591 A JP 13098591A JP 13098591 A JP13098591 A JP 13098591A JP H04356504 A JPH04356504 A JP H04356504A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- syndiotactic
- stereoregularity
- propylene
- compound
- 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 description 29
- 239000004743 Polypropylene Substances 0.000 title claims description 25
- 229920001155 polypropylene Polymers 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 5
- 150000003623 transition metal compounds Chemical class 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 239000000852 hydrogen donor Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 150000002899 organoaluminium compounds Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- PGOXJIBERNIRFR-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PGOXJIBERNIRFR-UHFFFAOYSA-L 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はシンジオタクチック構造
のポリプロピレンの立体規則性の低下方法に関する。詳
しくは特定の立体規則性の乱れをポリマー鎖中に導入す
る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reducing the stereoregularity of polypropylene having a syndiotactic structure. More specifically, it relates to a method for introducing a specific stereoregular disorder into a polymer chain.
【０００２】0002
【従来の技術】アイソタクチックポリプロピレンは安価
でしかも物性のバランスが比較的良好であり種々の用途
に利用されている。一方シンジオタクチックポリプロピ
レンについては古くよりその存在は知られていたが、従
来のバナジウム化合物とエーテルおよび有機アルミニウ
ムからなる触媒で低温重合する方法はシンジオタクティ
シティーが悪く、エラストマー的な特性を有すると言わ
れていたが、それが本来的にシンジオタクチックなポリ
プロピレンの特徴を表しているとは言い難かった。BACKGROUND OF THE INVENTION Isotactic polypropylene is inexpensive and has a relatively good balance of physical properties, and is used for various purposes. On the other hand, the existence of syndiotactic polypropylene has been known for a long time, but the conventional method of low-temperature polymerization using a catalyst consisting of a vanadium compound, ether, and organoaluminum has poor syndiotacticity, and it is thought that it has elastomer-like properties. However, it was difficult to say that this represented the inherently syndiotactic characteristics of polypropylene.
【０００３】これに対して、Ｊ．Ａ．ＥＷＥＮらにより
非対称な配位子を有する遷移金属化合物とアルミノキサ
ンからなる触媒によってシンジオタクチックペンタッド
分率が０．７ を越えるようなタクティシティーの良好
なポリプロピレンを得られることが初めて発見された（
Ｊ． Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９８８，１１０，
６２５５−６２５６）。この立体規則性の良好なシンジ
オタクチックポリプロピレンは剛性と耐衝撃性のバラン
スに優れており、従来のアイソタクチックなポリプロピ
レンの用途にも充分に利用可能なレベルであるが、用途
によっては立体規則性の乱れを制御してポリマー鎖中に
導入することで物性を変えることが望まれる。[0003] On the other hand, J. A. EWEN et al. discovered for the first time that polypropylene with good tacticity, with a syndiotactic pentad fraction exceeding 0.7, could be obtained using a catalyst consisting of a transition metal compound with an asymmetrical ligand and aluminoxane (
J. Am. Chem. Soc. , 1988, 110,
6255-6256). This syndiotactic polypropylene with good stereoregularity has an excellent balance of rigidity and impact resistance, and is at a level that can be used for conventional isotactic polypropylene applications. It is desired to change the physical properties by controlling the disorder of properties and introducing it into the polymer chain.
【０００４】0004
【発明が解決しようとする課題】重合反応で立体規則性
の低下を実現するには、重合温度を上げたり、立体規則
性の低い触媒を使用する方法などがあるが、規則的な乱
れをポリマー鎖中に導入することは極めて困難である。Problems to be Solved by the Invention: There are methods to reduce stereoregularity in polymerization reactions, such as increasing the polymerization temperature and using catalysts with low stereoregularity. It is extremely difficult to introduce into chains.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記問題を
解決して実質的にシンジオタクチック構造のポリプロピ
レンのポリマー鎖中に特定の乱れを導入する方法につい
て鋭意探索し本発明を完成した。[Means for Solving the Problems] The present inventors have completed the present invention by intensively searching for a method for solving the above problems and introducing specific disorder into the polymer chains of polypropylene having a substantially syndiotactic structure. .
【０００６】即ち本発明は、実質的にシンジオタクチッ
ク構造であるポリプロピレンに酸素の不存在下に１００
℃以下の温度で放射線を照射し、ついで水素供与性の
化合物で処理することでメソトリアッドを形成すること
を特徴とするシンジオタクチックポリプロピレンの立体
規則性の低下方法である。That is, the present invention provides polypropylene having a substantially syndiotactic structure with 100% polypropylene in the absence of oxygen.
This is a method for reducing the stereoregularity of syndiotactic polypropylene, which is characterized by forming mesotriads by irradiating with radiation at a temperature of .degree. C. or lower and then treating with a hydrogen-donating compound.
【０００７】本発明において実質的にシンジオタクチッ
ク構造のポリプロピレンとは、シンジオタクチック構造
のプロピレンの単独重合体のみならず、プロピレンと他
のオレフィンとの共重合体をも含み、特にシンジオタク
チックペンタッド分率が０．８を越える様な高度にシン
ジオタクチック構造のものに適用すれば、規則的な立体
的な乱れを導入することができ好ましい。[0007] In the present invention, polypropylene having a substantially syndiotactic structure includes not only a homopolymer of propylene having a syndiotactic structure, but also a copolymer of propylene and other olefins, and particularly polypropylene having a syndiotactic structure. If applied to a highly syndiotactic structure with a pentad fraction exceeding 0.8, regular steric disorder can be introduced, which is preferable.
【０００８】シンジオタクチックポリプロピレンを製造
するに用いる触媒としては、非対称な配位子を有する遷
移金属化合物と有機アルミニウムからなる触媒が用いら
れ、具体的には、上記文献に記載された化合物が例示で
きるが、異なる構造の触媒であっても、シンジオタクチ
ックペンタッド分率が０．８ 以上のポリプロピレンを
製造することができるものであれば利用できる。[0008] Catalysts used to produce syndiotactic polypropylene include catalysts consisting of a transition metal compound having an asymmetrical ligand and an organoaluminium; specifically, the compounds described in the above-mentioned literature are exemplified. However, catalysts with different structures can be used as long as they can produce polypropylene having a syndiotactic pentad fraction of 0.8 or more.
【０００９】非対称な配位子を有する遷移金属化合物と
しては上記文献に記載されたイソプロピル（シクロペン
タジエニル−１− フルオレニル） ハフニウムジクロ
リド、あるいはイソプロピル（シクロペンタジエニル−
１− フルオレニル） ジルコニウムジクロリドなどが
例示され、また有機アルミニウムとしては好ましくはア
ルミノキサンが用いられ、トリアルキルアルミニウムと
水との反応で合成される重合度５以上のアルミノキサン
が利用される。Examples of transition metal compounds having an asymmetric ligand include isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, or isopropyl (cyclopentadienyl-1-fluorenyl) described in the above-mentioned literature.
Examples include 1-fluorenyl) zirconium dichloride, and as the organoaluminum, aluminoxane is preferably used, and an aluminoxane with a degree of polymerization of 5 or more synthesized by the reaction of trialkylaluminium and water is used.
【００１０】上記遷移金属化合物に対するアルミノキサ
ンの使用割合としては１０〜１００００００モル倍、通
常５０〜５０００モル倍である。The ratio of aluminoxane to the above-mentioned transition metal compound is 10 to 1,000,000 times by mole, usually 50 to 5,000 times by mole.
【００１１】また重合条件については特に制限はなく不
活性媒体を用いる溶媒重合法、或いは実質的に不活性媒
体の存在しない塊状重合法、気相重合法も利用できる。
重合温度としては−１００ 〜２００ ℃、重合圧力と
しては常圧〜１００ ｋｇ／ｃｍ２ で行うのが一般的
である。好ましくは−１００ 〜１００ ℃、常圧〜５
０ｋｇ／ｃｍ２ である。[0011] There are no particular restrictions on the polymerization conditions, and solvent polymerization using an inert medium, bulk polymerization in which an inert medium is not substantially present, and gas phase polymerization can also be used. Generally, the polymerization temperature is -100 to 200 DEG C., and the polymerization pressure is normal pressure to 100 kg/cm2. Preferably -100 to 100°C, normal pressure to 5
0 kg/cm2.
【００１２】好ましい分子量としては、１３５ ℃テト
ラリン溶液で測定した極限粘度として０．１ 〜１０．
０程度であるのが一般的であり、特に分子量分布が狭い
重合体に適用すると分子量の低下が起こらず好ましい。The preferable molecular weight is 0.1 to 10.0 as the intrinsic viscosity measured in a tetralin solution at 135°C.
It is generally about 0, and is particularly preferable when applied to a polymer with a narrow molecular weight distribution, since no reduction in molecular weight occurs.
【００１３】シンジオタクチック構造の程度としてはプ
ロピレン単独重合体ではシンジオタクチックペンタッド
分率として０．７ 以上、好ましくは０．８ 以上であ
る。０．７ より小さいものでは、元々の規則性の乱れ
が大きく規則的な乱れを導入するという発明の効果が小
さい。また他のオレフィンとの共重合体であっても側鎖
が規則的に交互になっている、広義のシンジオ構造であ
るのが好ましく、上記単独重合体で高度にシンジオタク
チック構造を与える条件で共重合したものが好ましく利
用される。Regarding the degree of syndiotactic structure, the syndiotactic pentad fraction in the propylene homopolymer is 0.7 or more, preferably 0.8 or more. If it is smaller than 0.7, the original regularity is greatly disturbed and the effect of the invention of introducing regular disturbance is small. Even if the copolymer is a copolymer with other olefins, it is preferable to have a syndiotactic structure in a broad sense, in which the side chains are regularly alternating. A copolymerized one is preferably used.
【００１４】共重合に用いる他のオレフィンとしてはエ
チレンの他に炭素数４ 〜２０程度のα− オレフィン
が利用できる。好ましくは、ブテン−１、ペンテン−１
、ヘキセン−１、オクテン−１、４−メチルペンテン−
１などが例示される。プロピレンに対する重合の割合と
しては通常２０ｗｔ％ 以下、より好ましくは１０ｗｔ
％ 以下の他のオレフィンが共重合する条件で重合され
る。Other olefins used in the copolymerization include, in addition to ethylene, α-olefins having about 4 to 20 carbon atoms. Preferably butene-1, pentene-1
, hexene-1, octene-1, 4-methylpentene-
1 etc. are exemplified. The polymerization ratio to propylene is usually 20 wt% or less, more preferably 10 wt%.
% or less of other olefins are copolymerized.
【００１５】本発明において放射線の照射は酸素の不存
在下、すなわち、真空あるいは、窒素、ヘリウム、アル
ゴンなどの不活性ガス雰囲気で照射され、照射の際の温
度としては、１００ ℃以下であるのが好ましい。また
放射線の照射後に残っているラジカルは水素供与性の化
合物と接触することでラジカルが消滅することが必要で
ある。In the present invention, radiation is irradiated in the absence of oxygen, that is, in a vacuum or in an inert gas atmosphere such as nitrogen, helium, or argon, and the temperature during irradiation is 100° C. or less. is preferred. Further, it is necessary that the radicals remaining after radiation irradiation are annihilated by contacting with a hydrogen-donating compound.
【００１６】本発明において、重要なのは、主鎖が切断
され難い比較的低温で放射線を照射し、しかも照射後ま
で残っているラジカルは、他のラジカルとカップリング
、あるいは不飽和基を持つ部分と反応して分子量が増大
しない様に水素供与性の化合物、例えば、ヒドロキシル
基、アミノ基、チオール基など水素供与性の基を有する
化合物で処理して消滅させることである。What is important in the present invention is that the radiation is irradiated at a relatively low temperature where the main chain is difficult to cleave, and that the radicals remaining after irradiation are coupled with other radicals or with moieties having unsaturated groups. This is done by treating with a hydrogen-donating compound, for example, a compound having a hydrogen-donating group such as a hydroxyl group, an amino group, or a thiol group, so that the molecular weight does not increase due to the reaction.
【００１７】ここで接触処理の方法としては、照射した
ポリプロピレンを水素供与性の化合物の溶液の中に入れ
必要に応じ攪拌して処理するか、水素供与性の化合物の
蒸気に触れさせることで行われる。処理時間としてはポ
リプロピレンの形状にもよるが、通常数分〜数時間であ
る。The contact treatment can be carried out by placing the irradiated polypropylene in a solution of a hydrogen-donating compound and stirring as necessary, or by exposing it to the vapor of a hydrogen-donating compound. be exposed. Although the treatment time depends on the shape of the polypropylene, it is usually several minutes to several hours.
【００１８】本発明において、放射線としてはγ線、電
子線、Ｘ線、加速イオンなどが例示できるが、特に透過
性の大きいγ線、Ｘ線が好ましく利用でき、電子線を用
いる場合にはポリプロピレンを薄くして照射することが
好ましい。照射の際の線量としては０．１ 〜５０Ｍｒ
ａｄ、通常１ 〜１０Ｍｒａｄ程度で充分である。In the present invention, examples of radiation include gamma rays, electron beams, X-rays, accelerated ions, etc., but gamma rays and It is preferable to irradiate with a thin layer. The dose during irradiation is 0.1 ~ 50 Mr
ad, usually about 1 to 10 Mrad is sufficient.
【００１９】[0019]
【実施例】以下に実施例を示しさらに本発明を説明する
。[Examples] The present invention will be further explained by showing examples below.
【００２０】実施例１
常法にしたがって合成したイソプロピルシクロペンタジ
エニル−１− フルオレンをリチウム化し、四塩化ジル
コニウムと反応し再結晶することで得たイソプロピル（
シクロペンタジエニル−１− フルオレニル） ジルコ
ニウムジクロリド０．２ｇと東ソー・アクゾ（株）製メ
チルアルミノキサン（重合度１６．１）３０ｇ を用い
、内容積２００ リットルのオートクレーブで、プロピ
レンを挿入することで重合圧力３ｋｇ／ｃｍ２−Ｇ に
保って２０℃で２時間重合し、ついでメタノールとアセ
ト酢酸メチルで脱灰処理し塩酸水溶液で洗浄し、ついで
濾過して５．６ ｋｇのシンジオタクチックポリプロピ
レンを得た。Example 1 Isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method was lithiated, reacted with zirconium tetrachloride, and recrystallized to obtain isopropyl (
Polymerization was carried out using 0.2 g of zirconium dichloride (cyclopentadienyl-1-fluorenyl) and 30 g of methylaluminoxane (polymerization degree 16.1) manufactured by Tosoh Akzo Co., Ltd. in an autoclave with an internal volume of 200 liters by inserting propylene. Polymerization was carried out at 20°C for 2 hours while maintaining the pressure at 3 kg/cm2-G, followed by deashing with methanol and methyl acetoacetate, washing with an aqueous hydrochloric acid solution, and filtration to obtain 5.6 kg of syndiotactic polypropylene. .
【００２１】このポリプロピレンは１３Ｃ−ＮＭＲ に
よればシンジオタクチックペンタッド分率は０．９３５
であり、１３５ ℃テトラリン溶液で測定した極限粘
度（以下ηと略記） は１．４５、１，２，４−トリク
ロロベンゼンで測定した重量平均分子量と数平均分子量
との比（以下、ＭＷ／ＭＮ と略記）は２．２ であっ
た。According to 13C-NMR, this polypropylene has a syndiotactic pentad fraction of 0.935.
The intrinsic viscosity (hereinafter abbreviated as η) measured in a tetralin solution at 135°C is 1.45, and the ratio of the weight average molecular weight and number average molecular weight measured in 1,2,4-trichlorobenzene (hereinafter MW/MN) is 1.45. ) was 2.2.
【００２２】このポリプロピレンをガラス管に脱気封入
して２０℃でγ線を２Ｍｒａｄ／ｈｒで３Ｍｒａｄ照射
し、次いで窒素雰囲気でメタノールを加えて２４時間接
触処理した。処理後のパウダーのηは１．４４でありＭ
Ｗ／ＭＮ は２．４ であった。
また１３Ｃ−ＮＭＲ によればシンジオタクチックペン
タッド分率は０．９０６ でありｒｒｒｍ、ｍｍｒｒ、
ｒｍｍｒ、が略２：２：１で増加しており、その他の結
合の増加がほとんど見られず、ｍｍダイアッドだけが増
加しており、プロピレン単位１００ 個あたり約０．６
個のｍｍダイアッドの増加に相当する。照射前のポリ
マーのＤＳＣ で測定した融点が１５２ ℃であったの
に対し１４５℃と約７℃融点を低下させることができた
。[0022] This polypropylene was degassed and sealed in a glass tube and irradiated with gamma rays at 2 Mrad/hr for 3 Mrad at 20°C, followed by contact treatment with methanol added in a nitrogen atmosphere for 24 hours. The η of the powder after treatment is 1.44, and M
W/MN was 2.4. According to 13C-NMR, the syndiotactic pentad fraction is 0.906, rrrm, mmrr,
rmmr, increases at a ratio of approximately 2:2:1, with almost no increase seen in other bonds, only mm dyads increase, approximately 0.6 per 100 propylene units.
This corresponds to an increase in mm dyads. While the melting point of the polymer measured by DSC before irradiation was 152°C, it was possible to lower the melting point by about 7°C to 145°C.
【００２３】実施例２
実施例１ で得たポリプロピレンを ２００℃で溶融プ
レスして１ｍｍ のシートとした。このシートに電子線
照射装置（ 日新ハイボルテ−ジ（株）製ＥＰＳ−７５
０）を用いて窒素気流下で５Ｍｒａｄ 照射した。照射
後窒素下でメタノールで２４時間接触処理した。処理後
のηは１．４６であり、１３Ｃ−ＮＭＲ によればシン
ジオタクチックペンタッド分率は０．９０１ でありｒ
ｒｒｍ、ｍｍｒｒ、ｒｍｍｒ、が略２：２：１で増加し
ており、その他の結合の増加がほとんど見られず、ｍｍ
ダイアッドだけが増加していた。Example 2 The polypropylene obtained in Example 1 was melt-pressed at 200°C to form a 1 mm sheet. This sheet was coated with an electron beam irradiation device (EPS-75 manufactured by Nisshin High Voltage Co., Ltd.).
0) under a nitrogen stream at 5 Mrad. After irradiation, contact treatment was performed with methanol under nitrogen for 24 hours. After treatment, η is 1.46, and according to 13C-NMR, the syndiotactic pentad fraction is 0.901, and r
rrm, mmrr, rmmr, increased at a ratio of approximately 2:2:1, with almost no increase seen in other bonds, mm
Only dyads were increasing.
【００２４】[0024]
【発明の効果】本発明の方法はシンジオタクチック構造
のポリプロピレンのタクティシティーを規則的に低下す
ることができ、融点を低下させるなど工業的に極めて価
値がある。INDUSTRIAL APPLICABILITY The method of the present invention can regularly lower the tacticity of polypropylene having a syndiotactic structure, lowering the melting point, and is extremely valuable industrially.
Claims (1)
あるポリプロピレンに酸素の不存在下に１００ ℃以下
の温度で放射線を照射し、ついで水素供与性の化合物で
処理することでメソトリアッドを形成することを特徴と
するシンジオタクチックポリプロピレンの立体規則性の
低下方法。[Scope of Claims] [Claim 1] Polypropylene having a substantially syndiotactic structure is irradiated with radiation at a temperature of 100°C or less in the absence of oxygen, and then treated with a hydrogen-donating compound. A method for reducing the stereoregularity of syndiotactic polypropylene, which is characterized by forming mesotriads.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3130985A JP3053458B2 (en) | 1991-06-03 | 1991-06-03 | Method for reducing stereoregularity of syndiotactic polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3130985A JP3053458B2 (en) | 1991-06-03 | 1991-06-03 | Method for reducing stereoregularity of syndiotactic polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04356504A true JPH04356504A (en) | 1992-12-10 |
| JP3053458B2 JP3053458B2 (en) | 2000-06-19 |
Family
ID=15047225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3130985A Expired - Lifetime JP3053458B2 (en) | 1991-06-03 | 1991-06-03 | Method for reducing stereoregularity of syndiotactic polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3053458B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111798A (en) * | 2008-11-07 | 2010-05-20 | Mitsui Chemicals Inc | Modified resin composition |
-
1991
- 1991-06-03 JP JP3130985A patent/JP3053458B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111798A (en) * | 2008-11-07 | 2010-05-20 | Mitsui Chemicals Inc | Modified resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3053458B2 (en) | 2000-06-19 |
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