JPH038642B2 - - Google Patents
Info
- Publication number
- JPH038642B2 JPH038642B2 JP60050602A JP5060285A JPH038642B2 JP H038642 B2 JPH038642 B2 JP H038642B2 JP 60050602 A JP60050602 A JP 60050602A JP 5060285 A JP5060285 A JP 5060285A JP H038642 B2 JPH038642 B2 JP H038642B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- ethylene
- weight
- polypropylene resin
- block copolymer
- 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 - Lifetime
Links
- -1 propylene-ethylene Chemical group 0.000 claims description 54
- 239000004743 Polypropylene Substances 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 21
- 229920001400 block copolymer Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 150000001451 organic peroxides Chemical class 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- JDMGLOQMGRRGRD-UHFFFAOYSA-N 4,4-bis(tert-butylperoxy)pentanoic acid Chemical compound CC(C)(C)OOC(C)(CCC(O)=O)OOC(C)(C)C JDMGLOQMGRRGRD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
〔産業上の利用分野〕
本発明は改質ポリプロピレン樹脂の製造方法に
関し、詳しくは特定の性状を有するプロピレン−
エチレンブロツク共重合体を改質してなる流動
性、剛性および耐衝撃性のバランスの良好な光沢
のすぐれた改質ポリプロピレン樹脂の製造方法に
関する。
〔従来の技術及び発明が解決しようとする問題
点〕
従来から、プロピレン−エチレンブロツク共重
合体の諸物性、特に加工性や流動性を改善するた
めに、有機過酸化物で改質することが行なわれて
いる（特公昭51−30102号公報、特公昭58−7665
号公報、特開昭58−76444号公報）。
このうち特公昭51−30102号公報には、プロピ
レン−エチレン共重合部が全体の３〜30重量％で
あり、該共重合部のエチレン単位含量が30重量％
以上のプロピレン−エチレンブロツク共重合体を
改質する方法が開示されているが、ここで得られ
る改質ポリプロピレン樹脂組成物は光沢が不良で
あるとともに機械的物性が不充分なものであつ
た。
また、特公昭58−7665号公報に開示されている
方法は、全体のエチレン単位含量が５〜15重量
％、プロピレン−エチレン共重合部のエチレン単
位含量が50〜80重量％であり、かつ該共重合部の
極限粘度が４〜15であるプロピレン−エチレンブ
ロツク共重合体を改質するものである。しかし、
この方法によつて得られる改質ポリプロピレン樹
脂組成物は、光沢が低下し、また流動性、剛性と
耐衝撃性とのバランスが悪い。
さらに、特開昭58−76444号公報に示される方
法は、プロピレン−エチレン共重合部が全体の８
〜20重量％であり、かつ該共重合部のエチレン単
位含量が35〜60重量％であるプロピレン−エチレ
ンブロツク共重合体を、少量（10〜50ppm）の有
機過酸化物で改質するものであるが、得られる改
質ポリプロピレン樹脂組成物は、流動性に劣り、
また機械的強度が充分なものではなかつた。
そこで本発明者らは、上記従来技術の欠点を克
服し、流動性、剛性と耐衝撃性のバランスと光沢
にすぐれたポリプロピレン樹脂の製造方法を開発
すべく鋭意研究を重ねた。
〔問題点を解決するための手段〕
その結果、沸騰ヘプタン不溶部のアイソタクチ
ツクペンタツド分率、プロピレン−エチレン共重
合部の割合および該共重合部中のエチレン単位含
量を一定範囲に調節したプロピレン−エチレンブ
ロツク共重合体を用い、これを一定の分解度とな
るように改質することによつて、目的とする物性
を備えた改質ポリプロピレン樹脂が得られること
を見出した。本発明はこのような知見に基いて完
成したものである。
すなわち本発明は、主とししてプロピレン単独
重合部とプロピレン−エチレン共重合部よりな
り、かつ(A)沸騰ヘプタン不溶部のアイソタクチツ
クペンタツド分率が0.96以上、(B)全体に対するプ
ロピレン−エチレン共重合部の割合が３〜40重量
％および(C)プロピレン−エチレン共重合部のエチ
レン単位含量が該共重合部に対して10重量％以上
50重量％未満であり、メルトインデツクス（MI）
が0.5〜20ｇ／10分であるプロピレン−エチレン
ブロツク共重合体を、有機過酸化物の存在下に熱
処理して分解度1.2〜40の範囲に調節することを
特徴とする改質ポリプロピレン樹脂の製造方法を
提供するものである。
本発明において、改質前の樹脂としては、主と
してプロピレン単独重合部とプロピレン−エチレ
ン共重合部よりなり、かつ上述の(A)，(B)および(C)
の条件を備えたプロピレン−エチレンブロツク共
重合体が用いられる。
上記条件(A)は、沸騰ヘプタン不溶部のアイソタ
クチツクペンタツド分率が0.96以上、好ましくは
0.965以上、さらに好ましくは0.970以上となるこ
とである。0.96未満では得られる改質ポリプロピ
レン樹脂の剛性および熱変形温度が低下し、耐衝
撃性とのバランスがとれない。ここで、沸騰ヘプ
タン不溶部とは、用いるプロピレン−エチレンブ
ロツク共重合体を沸騰キシレンに完全に溶解させ
たのち、20℃に降温して４時間放置し、その後濾
過して不溶部を分離し、この不溶部を乾燥させて
から、さらに沸騰ヘプタンで８時間ソツクスレー
抽出して得られた抽出残渣を指称する。また、ア
イソタクチツクペンタツド分率とは、A.
ZambelliらによつてMacromolecules６，925
（1973）に発表されている方法により定義される。
これは13C−NMRを使用して測定されるポリプ
ロピレン分子鎖中のペンタツド単位でのアイソタ
クチツク連鎖、換言すればプロピレンモノマー単
位が５個連続してメソ結合した連鎖の中心にある
プロピレンモノマー単位の分率である。ただし、
13C−NMR吸収ピークの帰属に関しては、その
後発刊されたMacromolecules８，687（1975）に
基いて行なう。
次に条件(B)は、プロピレン−エチレンブロツク
共重合体全体に対するプロピレン−エチレン共重
合部の割合を３〜40重量％、好ましくは８〜35重
量％の範囲に調節することである。ここでプロピ
レン−エチレン共重合部の割合が３重量％未満で
は、得られる改質ポリプロピレン樹脂の耐衝撃性
が劣る。一方、40重量％を超えると剛性、熱変形
温度および光沢の低下した改質ポリプロピレン樹
脂となる。
さらに条件(C)は、プロピレン−エチレン共重合
部のエチレン単位含量が、該共重合部に対して10
重量％以上50重量％未満、好ましくは15重量％以
上50重量％未満となるように調節することであ
る。ここでエチレン単位含量が、10重量％未満で
は得られる改質ポリプロピレン樹脂の剛性や耐衝
撃性が低下し、逆に50重量％以上では光沢の著し
く低下したものとなる。
上記(A)，(B)および(C)の条件を満たしたプロピレ
ン−エチレンブロツク共重合体は様々な方法によ
り製造することができる。例えば三塩化チタンと
有機アルミニウム化合物とからなる触媒、またマ
グネシウム化合物に担持されたチタン複合体と有
機アルミニウム化合物および電子供与性化合物と
からなる触媒などを用いて、二段または三段以上
の多段重合法で製造することができる。さらに具
体的には、一段目でプロピレンのホモポリマーを
製造し、その後プロピレンモノマーを除去し、あ
るいは除去せずに二段目以降ではエチレンの存在
下、またはエチレンとプロピレンの共存下で重合
を進めることにより製造する。各段の圧力は数気
圧〜40気圧、温度は室温〜80℃とし、重合の形式
は溶液重合、スラリー重合、気相重合あるいはこ
れらの併合法が適用できる。なお、電子供与性化
合物、例えばアルコール類、アルデヒド類、エー
テル類、ラクトン類、ケトン類、アミン類、アミ
ド類、有機リン化合物、有機ケイ素化合物、チオ
ール類、チオエーテル類、チオエステル類などを
添加すると立体規則性が向上し、また必要に応じ
て水素を供給すれば分子量を調節することができ
る。なお、本発明で用いるプロピレン−エチレン
ブロツク共重合体は、MIが0.5〜20ｇ／10分のも
のである。
本発明の方法においては、このようにして得ら
れるプロピレン−エチレンブロツク共重合体を、
有機過酸化物の存在下に熱処理して、分解度1.2
〜40の範囲に調節する。ここで用いることのでき
る有機過酸化物としては、メチルエチルケトンパ
ーオキサイド、メチルイソブチルケトンパーオキ
サイド等のケトンパーオキサイド；ｎ−ブチル−
４，４−ビス（ｔ−ブチルパーオキシ）バレレイ
ト等のパーオキシケタール；クメンハイドロパー
オキサイド、ジイソプロピルベンゼンハイドロパ
ーオキサイド等のハイドロパーオキサイド；１，
３−ビス（ｔ−ビチルパーオキシイソプロピル）
ベンゼン、ジクミルパーオキサイド等のジアルキ
ルパーオキサイド；ベンゾイルパーオキサイド、
デカノイルパーオキサイド等のジアシルパーオキ
サイド；ビス−（４−ｔ−ブチルシクロヘキシル）
パーオキシジカーボネート等のパーカーボネー
ト；ｔ−ブチルパーオキシアセテート、ｔ−ブチ
ルパーオキシラウレート等のパーオキシエステル
などが挙げられるが、10時間半減期温度が100℃
以上で、かつ１分間半減期温度がプロピレン−エ
チレンブロツク共重合体の融点以上であることが
好ましい。このようなものとしては、クメンハイ
ドロパーオキサイド、ジイソプロピルベンゼンハ
イドロパーオキサイド、１，３−ビス（ｔ−ブチ
ルパーオキシイソプロピル）ベンゼン、ジクミル
パーオキサイドなどがある。
また、プロピレン−エチレンブロツク共重合体
の熱処理は、通常この共重合体の溶融温度以上、
分解温度未満において、該共重合体に上述の有機
過酸化物を適量加え、一軸押出機、二軸混練機、
ニーダー、バンバリーミキサー、ロール等で溶融
混練することにより行う。この際の熱処理条件は
分解度（即ち、改質前の樹脂のメルトインデツク
スと改質後の軸脂のメルトインデツクスとの比）
が1.2〜40、好ましくは1.5〜30の範囲になるよう
に選定すればよい。分解度が1.2未満では改質の
程度が小さく、得られる改質ポリプロピレン樹脂
組成物の流動性が充分なものとならないため加工
性に劣る。逆に40を超えると分解が進みすぎ、耐
衝撃性の低下したものとなる。
〔発明の効果〕
本発明の方法によれば、流動性、剛性と耐衝撃
性とのバランスが良好であるとともに、光沢の良
好な改質ポリプロピレン樹脂を得ることができ
る。
このようにして得られた改質ポリプロピレン樹
脂は、自動車部材、家電部材、農業資材をはじめ
各種産業資材として有効に利用される。
〔実施例〕
次に本発明を実施例により、さらに詳しく説明
する。
実施例１〜10および比較例１〜８
(1) プロピレン−エチレンブロツク共重合体の製
造
10容の撹拌機付きオートクレーブに乾燥ｎ−
ヘプタン４、三塩化チタン0.3ｇおよびジエチ
ルアルミニウムクロライド３ｇを仕込んだ。次い
で0.4〜0.8モル／モル−Tiの範囲で安息香酸メチ
ルを添加した（但し、比較例１では安息香酸メチ
ル無添加）。続いて水素を加え、その後昇温し、
65℃に保持しながらプロピレンを供給し、重合し
た。その後未反応のプロピレンを脱気し、次い
で、プロピレンとエチレンの混合ガスおよび水素
ガスを供給し、共重合した。共重合終了後、ブタ
ノールを添加し、濾過後、乾燥して白色のパウダ
ー状のプロピレン−エチレンブロツク共重合体を
得た。この共重合体の物性を第１表に示す。
(2) 改質ポリプロピレン樹脂の製造
上記(1)で得られたプロピレン−エチレンブロツ
ク共重合体に、所定量の１，３−ビス（ｔ−ブチ
ルパーオキシイソプロピル）ベンゼンを加え、均
一に混合して、220℃にて押出機で溶融混練して
改質ポリプロピレン樹脂のペレツトを得た。この
ペレツトを射出成形機で試験片を作成し、その物
性を調べた。結果を第１表に示す。
[Industrial Application Field] The present invention relates to a method for producing a modified polypropylene resin, and more specifically, the present invention relates to a method for producing a modified polypropylene resin.
This invention relates to a method for producing a modified polypropylene resin which is obtained by modifying an ethylene block copolymer and has a good balance of fluidity, rigidity and impact resistance, and has excellent gloss. [Prior art and problems to be solved by the invention] Conventionally, in order to improve the physical properties of propylene-ethylene block copolymers, especially their processability and fluidity, it has been possible to modify them with organic peroxides. (Special Publication No. 51-30102, Special Publication No. 58-7665)
(Japanese Patent Application Laid-open No. 58-76444). Among these, in Japanese Patent Publication No. 51-30102, the propylene-ethylene copolymerized portion accounts for 3 to 30% by weight of the total, and the ethylene unit content of the copolymerized portion is 30% by weight.
Although a method for modifying the propylene-ethylene block copolymer described above has been disclosed, the modified polypropylene resin composition obtained thereby had poor gloss and insufficient mechanical properties. Further, in the method disclosed in Japanese Patent Publication No. 58-7665, the total ethylene unit content is 5 to 15% by weight, the ethylene unit content of the propylene-ethylene copolymerized part is 50 to 80% by weight, and This method modifies a propylene-ethylene block copolymer whose copolymerization portion has an intrinsic viscosity of 4 to 15. but,
The modified polypropylene resin composition obtained by this method has reduced gloss and has a poor balance between fluidity, rigidity, and impact resistance. Furthermore, in the method shown in JP-A-58-76444, the propylene-ethylene copolymerization portion is 80% of the total.
~20% by weight, and a propylene-ethylene block copolymer whose ethylene unit content in the copolymerized portion is 35 to 60% by weight is modified with a small amount (10 to 50 ppm) of an organic peroxide. However, the resulting modified polypropylene resin composition has poor fluidity,
Moreover, the mechanical strength was not sufficient. Therefore, the present inventors have conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method for producing a polypropylene resin that has excellent balance between fluidity, rigidity and impact resistance, and excellent gloss. [Means for solving the problem] As a result, the isotactic pentad fraction of the boiling heptane insoluble part, the proportion of the propylene-ethylene copolymerized part, and the ethylene unit content in the copolymerized part were adjusted within a certain range. It has been discovered that a modified polypropylene resin having desired physical properties can be obtained by using a propylene-ethylene block copolymer and modifying it to a certain degree of decomposition. The present invention was completed based on this knowledge. That is, the present invention mainly consists of a propylene homopolymerization part and a propylene-ethylene copolymerization part, and (A) the isotactic pentad fraction of the boiling heptane-insoluble part is 0.96 or more, and (B) a propylene-ethylene copolymerization part with respect to the whole. The proportion of the ethylene copolymerization part is 3 to 40% by weight, and the ethylene unit content of the (C) propylene-ethylene copolymerization part is 10% by weight or more based on the copolymerization part.
less than 50% by weight, melt index (MI)
Production of a modified polypropylene resin characterized in that a propylene-ethylene block copolymer having a decomposition degree of 0.5 to 20 g/10 minutes is heat-treated in the presence of an organic peroxide to adjust the degree of decomposition to a range of 1.2 to 40. The present invention provides a method. In the present invention, the resin before modification mainly consists of a propylene homopolymerization part and a propylene-ethylene copolymerization part, and the above-mentioned (A), (B) and (C).
A propylene-ethylene block copolymer having the following conditions is used. The above condition (A) is such that the isotactic pentad fraction of the boiling heptane insoluble part is 0.96 or more, preferably
It should be 0.965 or more, more preferably 0.970 or more. If it is less than 0.96, the rigidity and heat distortion temperature of the resulting modified polypropylene resin will decrease, making it impossible to maintain a balance with impact resistance. Here, the boiling heptane insoluble parts are obtained by completely dissolving the propylene-ethylene block copolymer to be used in boiling xylene, lowering the temperature to 20°C, leaving it for 4 hours, and then filtering to separate the insoluble parts. This term refers to the extraction residue obtained by drying this insoluble portion and then Soxhlet extraction with boiling heptane for 8 hours. Also, isotactic pentad fraction is A.
Macromolecules 6 , 925 by Zambelli et al.
(1973).
This is an isotactic chain of pentad units in a polypropylene molecular chain measured using 13 C-NMR, in other words, the proportion of a propylene monomer unit at the center of a chain of five consecutive meso-bonded propylene monomer units. rate. however,
The assignment of 13 C-NMR absorption peaks is based on Macromolecules 8 , 687 (1975), which was subsequently published. Next, condition (B) is to adjust the proportion of the propylene-ethylene copolymer portion to the entire propylene-ethylene block copolymer to be in the range of 3 to 40% by weight, preferably 8 to 35% by weight. If the proportion of the propylene-ethylene copolymerized portion is less than 3% by weight, the resulting modified polypropylene resin will have poor impact resistance. On the other hand, if it exceeds 40% by weight, the modified polypropylene resin will have reduced rigidity, heat distortion temperature, and gloss. Furthermore, condition (C) is such that the ethylene unit content of the propylene-ethylene copolymerization portion is 10% relative to the copolymerization portion.
It is adjusted to be at least 15% by weight and less than 50% by weight, preferably at least 15% by weight and less than 50% by weight. If the ethylene unit content is less than 10% by weight, the resulting modified polypropylene resin will have lower rigidity and impact resistance, and if it is more than 50% by weight, the gloss will be significantly reduced. Propylene-ethylene block copolymers satisfying the above conditions (A), (B) and (C) can be produced by various methods. For example, using a catalyst made of titanium trichloride and an organoaluminum compound, or a catalyst made of a titanium composite supported on a magnesium compound, an organoaluminum compound, and an electron-donating compound, etc. It can be manufactured legally. More specifically, a propylene homopolymer is produced in the first stage, and then the propylene monomer is removed, or the propylene monomer is not removed and the polymerization proceeds in the presence of ethylene or the coexistence of ethylene and propylene in the second and subsequent stages. Manufactured by The pressure at each stage is from several atm to 40 atm, the temperature from room temperature to 80°C, and the polymerization format can be solution polymerization, slurry polymerization, gas phase polymerization, or a combination of these. Note that when electron-donating compounds such as alcohols, aldehydes, ethers, lactones, ketones, amines, amides, organophosphorus compounds, organosilicon compounds, thiols, thioethers, and thioesters are added, steric The regularity is improved, and the molecular weight can be adjusted by supplying hydrogen as necessary. The propylene-ethylene block copolymer used in the present invention has an MI of 0.5 to 20 g/10 min. In the method of the present invention, the propylene-ethylene block copolymer thus obtained is
Heat treated in the presence of organic peroxides to a degree of decomposition of 1.2
Adjust to a range of ~40. Examples of organic peroxides that can be used here include ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide;
Peroxyketals such as 4,4-bis(t-butylperoxy)valerate; Hydroperoxides such as cumene hydroperoxide and diisopropylbenzene hydroperoxide; 1,
3-bis(t-bitylperoxyisopropyl)
Dialkyl peroxide such as benzene and dicumyl peroxide; benzoyl peroxide,
Diacyl peroxide such as decanoyl peroxide; bis-(4-t-butylcyclohexyl)
Percarbonates such as peroxydicarbonate; peroxyesters such as t-butylperoxyacetate and t-butylperoxylaurate, but have a 10-hour half-life temperature of 100°C
It is preferable that the 1-minute half-life temperature is equal to or higher than the melting point of the propylene-ethylene block copolymer. These include cumene hydroperoxide, diisopropylbenzene hydroperoxide, 1,3-bis(t-butylperoxyisopropyl)benzene, dicumyl peroxide, and the like. In addition, heat treatment of propylene-ethylene block copolymer is usually carried out at a temperature higher than the melting temperature of this copolymer.
At a temperature below the decomposition temperature, an appropriate amount of the above-mentioned organic peroxide is added to the copolymer, and the mixture is processed using a single-screw extruder, a twin-screw kneader,
This is carried out by melt-kneading using a kneader, Banbury mixer, roll, etc. The heat treatment conditions at this time are the degree of decomposition (i.e., the ratio of the melt index of the resin before modification to the melt index of the shaft fat after modification)
is in the range of 1.2 to 40, preferably 1.5 to 30. If the degree of decomposition is less than 1.2, the degree of modification is small and the resulting modified polypropylene resin composition does not have sufficient fluidity, resulting in poor processability. On the other hand, if it exceeds 40, decomposition progresses too much, resulting in a product with reduced impact resistance. [Effects of the Invention] According to the method of the present invention, it is possible to obtain a modified polypropylene resin that has a good balance between fluidity, rigidity, and impact resistance, and also has good gloss. The modified polypropylene resin thus obtained can be effectively used as various industrial materials including automobile parts, household appliance parts, and agricultural materials. [Example] Next, the present invention will be explained in more detail with reference to Examples. Examples 1 to 10 and Comparative Examples 1 to 8 (1) Production of propylene-ethylene block copolymer In a 10-volume autoclave equipped with a stirrer, dry n-
4 g of heptane, 0.3 g of titanium trichloride, and 3 g of diethylaluminum chloride were charged. Next, methyl benzoate was added in a range of 0.4 to 0.8 mol/mol-Ti (however, in Comparative Example 1, methyl benzoate was not added). Next, add hydrogen, then raise the temperature,
Propylene was supplied and polymerized while maintaining the temperature at 65°C. Thereafter, unreacted propylene was degassed, and then a mixed gas of propylene and ethylene and hydrogen gas were supplied to carry out copolymerization. After the copolymerization was completed, butanol was added, filtered, and dried to obtain a white powdery propylene-ethylene block copolymer. The physical properties of this copolymer are shown in Table 1. (2) Production of modified polypropylene resin A predetermined amount of 1,3-bis(t-butylperoxyisopropyl)benzene was added to the propylene-ethylene block copolymer obtained in (1) above and mixed uniformly. The mixture was melt-kneaded using an extruder at 220°C to obtain modified polypropylene resin pellets. Test pieces were made from the pellets using an injection molding machine, and their physical properties were investigated. The results are shown in Table 1.
【表】【table】
Claims (1)
ン−エチレン共重合部よりなり、かつ(A)沸騰ヘプ
タン不溶部のアイソタクチツクペンタツド分率が
0.96以上、(B)全体に対するプロピレン−エチレン
共重合部の割合が３〜40重量％および(C)プロピレ
ン−エチレン共重合部のエチレン単位含量が該共
重合部に対して10重量％以上50重量％未満であ
り、メルトインデツクス（MI）が0.5〜20ｇ／10
分であるプロピレン−エチレンブロツク共重合体
を、有機過酸化物の存在下に熱処理して分解度
1.2〜40の範囲に調節することを特徴とする改質
ポリプロピレン樹脂の製造方法。1 It mainly consists of a propylene homopolymerization part and a propylene-ethylene copolymerization part, and (A) the isotactic pentad fraction of the boiling heptane insoluble part is
0.96 or more, (B) the ratio of the propylene-ethylene copolymerized part to the whole is 3 to 40% by weight, and (C) the ethylene unit content of the propylene-ethylene copolymerized part is 10% or more by weight to the copolymerized part 50% % and the melt index (MI) is 0.5-20g/10
A propylene-ethylene block copolymer, which is a polymer, is heat-treated in the presence of an organic peroxide to reduce decomposition.
A method for producing a modified polypropylene resin, the method comprising adjusting the polypropylene resin to a range of 1.2 to 40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5060285A JPS61211306A (en) | 1985-03-15 | 1985-03-15 | Modified polypropylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5060285A JPS61211306A (en) | 1985-03-15 | 1985-03-15 | Modified polypropylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61211306A JPS61211306A (en) | 1986-09-19 |
| JPH038642B2 true JPH038642B2 (en) | 1991-02-06 |
Family
ID=12863512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5060285A Granted JPS61211306A (en) | 1985-03-15 | 1985-03-15 | Modified polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61211306A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9915469B1 (en) * | 1998-08-20 | 2009-01-13 | crystalline propylene copolymer compositions, process for preparing copolymer compositions and monolayer or multilayer film or sheet comprising said polymeric compositions. | |
| KR20020046389A (en) * | 2000-12-13 | 2002-06-21 | 유현식 | Polypropylene-based resin composition |
| US6855771B2 (en) | 2002-10-31 | 2005-02-15 | Grant Doney | Process for making block polymers or copolymers from isotactic polypropylene |
| AU2005214953A1 (en) * | 2004-02-18 | 2005-09-01 | Stratek Plastic Limited | Process for incorporating substances into polymeric materials in a controllable manner |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5130102A (en) * | 1974-09-06 | 1976-03-15 | Komatsu Mfg Co Ltd | HIKENINSHIKISUKU REEPANOJIDOSEIDOSOCHI |
| JPS5379988A (en) * | 1976-12-21 | 1978-07-14 | Dart Ind Inc | Molding composite with shockkresistance at low temperature |
| JPS55139447A (en) * | 1979-04-06 | 1980-10-31 | Chisso Corp | Modification of propylene-ethylene block copolymer |
| JPS5747305A (en) * | 1980-09-04 | 1982-03-18 | Sumitomo Chem Co Ltd | Modifying method of polypropylene |
| JPS5876444A (en) * | 1981-10-30 | 1983-05-09 | Mitsubishi Chem Ind Ltd | Modifying method of propylene-ethylene block copolymer |
| JPS58201816A (en) * | 1982-05-19 | 1983-11-24 | Chisso Corp | Propylene-ethylene block copolymer for molded article having high rigidity and its preparation |
| JPS6081206A (en) * | 1983-10-11 | 1985-05-09 | Ube Ind Ltd | Modified polypropylene |
-
1985
- 1985-03-15 JP JP5060285A patent/JPS61211306A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5130102A (en) * | 1974-09-06 | 1976-03-15 | Komatsu Mfg Co Ltd | HIKENINSHIKISUKU REEPANOJIDOSEIDOSOCHI |
| JPS5379988A (en) * | 1976-12-21 | 1978-07-14 | Dart Ind Inc | Molding composite with shockkresistance at low temperature |
| JPS55139447A (en) * | 1979-04-06 | 1980-10-31 | Chisso Corp | Modification of propylene-ethylene block copolymer |
| JPS5747305A (en) * | 1980-09-04 | 1982-03-18 | Sumitomo Chem Co Ltd | Modifying method of polypropylene |
| JPS5876444A (en) * | 1981-10-30 | 1983-05-09 | Mitsubishi Chem Ind Ltd | Modifying method of propylene-ethylene block copolymer |
| JPS58201816A (en) * | 1982-05-19 | 1983-11-24 | Chisso Corp | Propylene-ethylene block copolymer for molded article having high rigidity and its preparation |
| JPS6081206A (en) * | 1983-10-11 | 1985-05-09 | Ube Ind Ltd | Modified polypropylene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61211306A (en) | 1986-09-19 |
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