JPH0244846B2 - - Google Patents
Info
- Publication number
- JPH0244846B2 JPH0244846B2 JP56032216A JP3221681A JPH0244846B2 JP H0244846 B2 JPH0244846 B2 JP H0244846B2 JP 56032216 A JP56032216 A JP 56032216A JP 3221681 A JP3221681 A JP 3221681A JP H0244846 B2 JPH0244846 B2 JP H0244846B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- titanium
- ethylene
- titanium trichloride
- polymerization
- 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 60
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 34
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical group Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 31
- -1 propylene-ethylene Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 24
- 238000007334 copolymerization reaction Methods 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 229920001400 block copolymer Polymers 0.000 claims description 14
- 239000011949 solid catalyst Substances 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920001384 propylene homopolymer Polymers 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000011344 liquid material Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 41
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 239000007789 gas Substances 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 241000251468 Actinopterygii Species 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ZMXPNWBFRPIZFV-UHFFFAOYSA-M dipropylalumanylium;chloride Chemical compound [Cl-].CCC[Al+]CCC ZMXPNWBFRPIZFV-UHFFFAOYSA-M 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910010062 TiCl3 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229940049953 phenylacetate Drugs 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- XDILCINHTMZTGG-UHFFFAOYSA-N 3-(3-dodecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(O)=O XDILCINHTMZTGG-UHFFFAOYSA-N 0.000 description 1
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
本発明はプロピレン−エチレンブロツク共重合
体の製造法に関する。
プロピレン単独重合体の耐衝撃性および低温脆
性を改良するためにプロピレン−エチレンブロツ
ク共重合体を製造する方法はよく知られており、
通常は三塩化チタンあるいはマグネシウム化合物
に担持した塩化チタンと有機アルミニウム化合物
からなるいわゆるチーグラー・ナツタ型触媒を用
いて不活性液状炭化水素あるいは液化プロピレン
のような希釈剤の存在下、第１段階でプロピレン
を重合させ、ついで第２段階で、第１段階で生成
したプロピレン重合体の存在下エチレンとプロピ
レンを共重合させてブロツク共重合体を得る方法
が用いられている。
重合方法としては回分法と連続法とがあるが、
回分法は一般的に生産性が低く、経済性に問題が
有りその上、製造ラン毎に製品の品質にフレが生
じるのはある程度避けられないといつた欠点を有
する。一方、連続法はこの様な欠点を有しないの
で工業的には有利な方法であるが、製品の品質面
では以下に述べる様に問題点が発生する。即ち、
上記した２段階の重合を、例えば第１段階を第１
反応槽、第１段階を第２反応槽として直列につな
ぎ、第１段階でプロピレンの重合を、第２段階で
プロピレンとエチレンの共重合を連続法で行なつ
た場合、生成するブロツク共重合体は、回分法の
ものに比べ低温脆性や耐衝撃性が悪化く、破断点
伸度が低下し、またその成形品にフイツシユ−ア
イが発生する。連続法でこの様な問題点が発生す
ることの主因として、以下のことが考えられる。
２個以上の反応器を直列につなぎ連続法で重合を
行つた場合、各反応器内はほゞ完全混合状態であ
ると考えられ従つて各反応器内の触媒あるいは触
媒を含む重合体の滞留時間に分布が生じる。滞留
時間の短い触媒からは触媒単位量当りの重合体の
生成量（以下、これを触媒効率という）の小さい
重合体が、逆に滞留時間の長い触媒からは触媒効
率の大きい重合体が生成する。各反応器でこの様
に触媒効率の小さいものから大きいものに至る重
合体が生成し、その結果全生成重合体の組成は分
布を有することになる。第２段階において生成し
たプロピレンとエチレンの共重合体（以下、これ
をEPRということがある）分率を、例えば15％
になるように各反応器の平均滞留時間を設定して
も実際に得られるブロツク共重合体中にはEPR
の分率が極端には０％に近い重合体粒子から、
100％に近い重合体粒子までが含まれることにな
る。この中でEPRの分率が比較的大きい重合体
粒子がプロピレン単独重合体に分散しなくなり成
形品にフイツシユ−アイが発生し、その結果低温
脆性や耐衝撃性等が悪化するものと考えられる。
この様な連続重合における問題点を解決するた
めに種々の方法が提案されている。
特公昭53−25585号および特開昭49−53990号に
おいては、多数の反応槽を使用する方法が提案さ
れている。この方法では、回分法で得られたもの
に近い物性を有するブロツク共重合体が得られる
が、槽数の増加の伴い、建設費が増加し経済的に
不利であるばかりでなく多槽化に伴い製品品質管
理が大変になり極力少い槽数にする必要がある。
特公昭44−19542号、特開昭55−115417号にお
いては第２段階のプロピレン−エチレン共重合時
に電子供与性化合物を添加する方法が提案されて
いる。しかし、この方法では本発明者らの検討に
よると充分に効果的であるとは言えないものであ
つた。
特開昭49−61278号においては第２段階のプロ
ピレン−エチレン共重合体の分子量を下げる方法
が提案されている。しかしこの方法は本発明者ら
の検討によると、成形品の耐衝撃性の低下をもた
らすものであつた。
本発明者らは以上の様な問題点を解決するため
に種々検討した結果、第２段階のプロピレン−エ
チレン共重合時に特定のアルミニウム化合物を添
加することによつてかかる問題点を大巾に改良出
来ることを見い出し本発明に到達した。
即ち、本発明は、チタン含有固体触媒成分と一
般式AlR1 nCl3-n（式中R1は炭素数１〜20の炭化水
素基を表わし、ｍは３≧ｍ＞1.5の数を示す）で
表わされる有機アルミニウム化合物とを主体とす
る触媒系を用い、第１段階においてプロピレン単
独またはプロピレンとエチレンとを気相中のプロ
ピレンとエチレンの和に対するプロピレン濃度が
90モル％以上である条件下で重合することによつ
てプロピレン単独重合体またはプロピレン−エチ
レン共重合体を製造し、第２段階において該触媒
系および第１段階で製造された重合体の存在下で
プロピレンとエチレンとを気相中のプロピレンと
エチレンの和に対するプロピレン濃度が90モル％
未満である条件下で共重合させてプロピレン−エ
チレンブロツク共重合体を連続的に製造する方法
において、該第２段階に、共重合速度の対時間減
衰を大きくする一般式AlR2 oX3-o（式中R2は炭素
数１〜20の炭化水素基を表わし、Ｘはハロゲン原
子を表わし、ｎは1.5≧ｎ≧０の数を示す）で表
わされるアルミニウム化合物をあらたに添加して
重合することを特徴とするプロピレン−エチレン
ブロツク共重合体の製造法に存する。
本発明方法において第２段階に特定のアルミニ
ウム化合物を添加することにより前記した如き改
良効果が発現する理由は明らかではないが第２段
階におけるプロピレン−エチレン共重合速度の対
時間減衰が特定のアルミニウム化合物の添加によ
つて拡大（強化）されることにより、EPRの分
率が比較的大きい重合体粒子の量が極端に減つた
ことに起因するものと考えられる。この様な効果
は、共重合速度の対時間減衰を大きくしたことに
よつてもたらされるものであり、後で比較例で示
すように、電子供与性化合物の如き触媒系に対す
る被毒物質を添加することによつて共重合速度の
対時間減衰を変えないで共重合速度そのものを小
さくしたり、あるいはトリアルキルアルミニウム
の如き活性化剤を添加して共重合速度の対時間減
衰を小さくしたりした場合には本発明方法におけ
るような効果はみられない。
さらに本発明を詳細に説明するに、本発明にお
いて使用される触媒系はチタン含有固体触媒成分
と有機アルミニウム化合物とから得られる。
チタン含有固体触媒成分としては、固体のマグ
ネシウム化合物、四ハロゲン化チタン及び電子供
与性化合物を接触させて得られる公知の担体担持
型触媒成分も使用可能であるが、好ましくは三塩
化チタンを主成分とするものである。三塩化チタ
ンを主成分とする固体触媒成分としては、四塩化
チタンを金属アルミニウム、水素または有機アル
ミニウム化合物で還元したもの、あるいはこれら
を摩砕したもの、さらにこれらを電子供与性化合
物と接触処理または粉砕処理したものも使用可能
であるが、特に好ましくは、アルミニウム含有量
がチタンに対するアルミニウムの原子比で0.15以
下、好ましくは0.1以下、さらに好ましくは0.02
以下であり、かつ錯化剤を含有するものである。
そして錯化剤の含有量は、固体三塩化チタン系触
媒系錯体中の三塩化チタンに対する錯化剤のモル
比で0.001以上、好ましくは0.01以上である。具
体的には、三塩化チタン、三塩化チタンのチタン
に対するアルミニウムの原子比で0.15以下の式
AlR3 pX3-p（式中、R3は炭素数１〜20の炭化水素
基、Ｘはハロゲン原子、ｐは０≦ｐ≦２の数を示
す）で表わされるハロゲン化アルミニウムおよび
三塩化チタンに対しモル比で0.001以上の錯化剤
を含むもの、例えば式TiCl3・（AlR3 pX3-p）s・
（Ｃ）t（式中R3は炭素数１〜20の炭化水素基であ
り、Ｘはハロゲン原子であり、ｐは０≦ｐ≦２の
数であり、Ｃは錯化剤であり、ｓは0.15以下の数
であり、ｔは0.001以上の数である）で表わされ
るものが挙げられるが、もちろん、TiCl3成分、
AlR3 pX3-p成分及び錯化剤Ｃ成分のほかに、少量
のヨウ素、三塩化チタンの塩素の一部または全部
がヨウ素もしくは臭素で置換されたもの、あるい
はMgCl2、MgO等の担体用無機固体、ポリエチ
レン、ポリプロピレン等のオレフイン重合体粉末
等を含むものであつてもよい。錯化剤Ｃとして
は、エーテル、チオエーテル、ケトン、カルボン
酸エステル、アミン、カルボン酸アミド、ポリシ
ロキサン等が挙げられるが、このうちエーテル又
はチオエーテルがとくに好ましい。エーテル又は
チオエーテルとしては、一般式R4−Ｏ−R5又は
R4−Ｓ−R5（式中、R4、R5は炭素数15以下の炭
化水素基を示す。）で表わされるものが挙げられ
る。AlR3 pX3-pとしては、AlCl3、AlR3Cl2等が挙
げられる。
しかしてこのような個体三塩化チタン系触媒錯
体は、
(イ) エーテル又はチオエーテルの存在下に液状化
した三塩化チタンを含有する液状物から150℃
以下の温度で析出させる
(ロ) 四塩化チタンを有機アルミニウム化合物又は
金属アルミニウムで還元して得られた個体三塩
化チタンを、錯化剤処理及びハロゲン化合物処
理する
などの方法により容易に製造することができる。
上記(イ)及び(ロ)の方法はすでに特公昭55−8451号、
同55−8452号、同53−24194号、同55−8003号、
同54−41040号、同54−28316号、特開昭53−
12796号、同52−91794号、同55−116626号、特公
昭53−3356号、同52−40348号等において公知で
ある。さらに(イ)、(ロ)の方法の外に、特公昭54−
27871号に記載されているように、四塩化チタン
を有機アルミニウム化合物で還元して得られる固
体三塩化チタンに、該三塩化チタンに対しモル比
0.5〜５のエーテル化合物を加えて、50〜120℃に
加熱し、次いで固体を分離することにより製造さ
れたものも使用しうる。
一方、第１段階及び第２段階で共触媒として使
用される有機アルミニウム化合物としては、一般
式AlR1 nCl3-n（式中、R1は炭素数１〜20の炭化水
素基を表わし、ｍは３≧ｍ＞1.5の数を示す）で
表わされる。チタン含有固体触媒成分が固体のマ
グネシウム化合物を含有する担体担持型触媒成分
である場合はAlR1 3またはAlR1 3とAlR1 2Clの混合
物を使用するのが好ましい。一方TiCl3を主成分
とする触媒成分である場合はAlR1 2Clを使用する
のが好ましい。この場合、R1がエチル基で示さ
れ、ｍが２の場合であるジエチルアルミニウムモ
ノクロライドも十分使用可能であるが、R1がノ
ルマルプロピル基又はノルマルヘキシル基である
ものがとくに好ましい。
第２段階であらたに添加するアルミニウム化合
物は、共重合速度の対時間減衰を大きくするもの
であり、一般式AlR2 oX3-o（式中、R3は炭素数１
〜20の炭化水素基を表わし、Ｘはハロゲン原子好
ましくは塩素を表わし、ｎは1.5≧ｎ≧０の数を
示す）で表わされる。この内、AlR2 1.5Cl1.5、
AlR2Cl2あるいはこれらの混合物を使用するのが
好ましい。この様な化合物としては具体的には
R2がメチル基、エチル基、プロピル基、イソプ
ロピル基、ブチル基、イソブチル基、ヘキシル
基、オクチル基、デシル基、ドデシル基等である
ものが挙げられる。特に好ましくは入手の容易さ
と取扱い易さからエチルアルミニウムダイクロラ
イド（AlEtCl2）、エチルアルミニウムセスキク
ロライド（AlEt1.5Cl1.5）およびこれらの混合物
が挙げられる。またAlCl3も使用できる。
触媒各成分の使用割合は、通常、チタン含有固
体触媒成分中のTi：AlR1 nCl3-nのモル比で１：
１〜100好ましくは１：２〜40の範囲から、
AlR1 nCl3-n：AlR2 oX3-oのモル比で１：0.01〜
0.50好ましくは１：0.03〜0.30の範囲から選ばれ
る。
更に本発明方法においては、上記触媒及び共触
媒のほかに触媒第３成分として公知の例えばカル
ボン酸エステル、亜リン酸エステル、アミンの如
き電子供与性化合物を使用してもよい。第３成分
の使用する場合には、同じくTi：第３成分のモ
ル比で、１：0.01〜10好ましくは１：0.05〜２に
なるように選ばれる。
なお、触媒として用いられるチタン含有固体触
媒成分は、そのまま重合に用いても良いが、有機
アルミニウム化合物の存在下、少量のプロピレン
あるいはエチレン等オレフインで前処理してから
使用するのが好ましい。この前処理は例えば嵩密
度など重合体のスラリー物性の改良に効果があ
る。
前処理は重合温度より低い温度、一般に20℃〜
60℃で、前処理によつて生成した重合体／固体触
媒成分＝0.1〜50／１（重量比）、通常１〜20／１
になる様に行なわれる。
本発明方法においては、上述のようなチタン含
有固体触媒成分および有機アルミニウム化合物を
主体とする触媒系を用いてプロピレン−エチレン
ブロツク共重合体を製造する方法において重合を
２段階に分けて行なわせるわけであるが、重合は
プロパン、ブタン、ヘキサン、ヘプタン、ベンゼ
ン、トルエンの如き不活性炭化水素希釈剤中で行
つてもよいし、液化プロピレン希釈剤中で行つて
もよい。またいわゆる気相重合で行つてもよい。
まず、第１段階では、少くともチタン含有固体
触媒成分と一般式AlR1 nCl3-nで表わされる有機
アルミニウム化合物とを用いて、プロピレンの単
独重合またはプロピレンとエチレンとを気相中の
プロピレン濃度（プロピレンのプロピレンとエチ
レンの和に対する濃度）が90モル％以上である条
件下で共重合を行う（以下、単にプロピレンの単
独重合と略すことがある）。通常、プロピレン単
独重合体の量は全重合体生成量の70〜95重量％と
なるように重合温度および重合時間が選ばれる。
重合温度は通常40〜100℃、好ましくは50〜80℃
の範囲から選ばれる。第１段階で得られるプロピ
レン単独重合体のメルトフローインデツクス（以
下、MFIと略す。）が、１〜150になるように重
合温度、分子量調節剤の量を選ぶ。分子量調節剤
としては水素、ジアルキル亜鉛等が挙げられる
が、好ましくは水素である。通常、気相における
水素濃度（水素のプロピレンとエチレンの和に対
する濃度）は約１〜30モル％である。
次に第２段階では、第１段階で生成したプロピ
レン単独重合体およびあらたに添加した一般式
AlR2 oX3-oで表わされるアルミニウム化合物の存
在下プロピレンとエチレンの共重合を行う。気相
中のプロピレン濃度は、90モル％未満であればよ
いが、好ましくは気相プロピレン濃度は50〜85モ
ル％である。この範囲では、非結晶性重合体の副
生量が最大となる条件であるが、一方最終重合体
の衝撃強度が最も改良される条件である。通常、
プロピレン−エチレン共重合体の量が全重合体生
成量の５〜30重量％となるように重合温度および
重合時間が選ばれる。この量が５重量％未満では
衝撃強度等改良の効果が小さく、30重量％を超え
ると、嵩密度および自由流動性が悪化し好ましく
ない。重合温度は通常25〜70℃好ましくは25〜65
℃の範囲から選ばれる。70℃を超えると、得られ
るプロピレン−エチレンブロツク共重合体は、自
由流動性が乏しく重合体粒子間の凝集が起り好ま
しくない。プロピレン−エチレン共重合体の
MFIは通常、0.1以下となるように重合温度、分
子量調整剤である水素の量を選ぶ。通常気相にお
ける水素濃度は、0.5〜30モル％とする。MFIが
0.1を越えると衝撃強度の改良が不充分となる。
また、MFIが極めて小さい場合、例えば10-7未満
の場合、衝撃強度の向上が大きく良好ではある
が、射出成型時のバラス効果が大となり、寸法安
定性が悪化し好ましくない。全重合体中のエチレ
ン含有量は、２〜30重量％が好ましい。
連続式の場合各段階は別々の重合槽が用いら
れ、第１段階の重合槽と第２段階の重合槽は直列
につながれる。もちろん各段階において、重合槽
は複数であつてもよく、例えば、第１段階の重合
を直列につないた２槽の重合槽でおこなつてもよ
い。重合槽間の重合体スラリーの移送は常法に従
い、例えば圧力差でおこなうか、スラリーポンプ
によりおこなうのが便利である。
以下、本発明を実施例によつて更に詳細に説明
するが、本発明はその要旨をこえない限り以下の
実施例に限定されるものではない。なお、実施例
中の略号の意味及び各種の測定方法は次の通りで
ある。
メルトフローインデツクスMFI（ｇ／10min）
はASTM D1238−70により、230℃、荷重2.16Kg
の時の重合体の押出量を示す。
第１降伏強度YS（Kg／cm2）及び破断点伸度UE
（％）はASTM D638−72に準拠し厚さ１mmのプ
レスシートから打ち抜いたダンペル片の引張試験
によつて求めた。特に断わらない限り20℃での測
定値である。アイゾツト衝撃強度（Kg−cm／cm）
はASTM D256により、厚さ５mmのプレスシー
トから打ち抜いた短冊片にノツチを入れたものに
ついて測定した。特に断わらない限り20℃での値
である。
脆化温度Tb（℃）はASTM D746により、厚さ
２mmの平板から打抜いた試験片について測定し
た。
フイツシユ・アイの評価は厚さ１mmのプレスシ
ートを折り曲げて、フイツシユ・アイの量を観察
し次の４つのランクに分類した。
The present invention relates to a method for producing propylene-ethylene block copolymers. Methods for producing propylene-ethylene block copolymers to improve the impact resistance and low-temperature brittleness of propylene homopolymers are well known.
Typically, a so-called Ziegler-Natsuta type catalyst consisting of titanium chloride or an organoaluminium compound supported on a titanium trichloride or magnesium compound is used to convert propylene in the first stage in the presence of a diluent such as an inert liquid hydrocarbon or liquefied propylene. A method is used in which a block copolymer is obtained by polymerizing ethylene and propylene in the second step in the presence of the propylene polymer produced in the first step. Polymerization methods include batch methods and continuous methods.
Batch methods generally have low productivity, are uneconomical, and have drawbacks such as unavoidable variation in product quality from production run to production run. On the other hand, the continuous method is industrially advantageous since it does not have such drawbacks, but it does have problems in terms of product quality as described below. That is,
The two-stage polymerization described above is carried out, for example, the first stage is
The block copolymer produced when the first stage of the reaction tank is connected in series as a second reaction tank and the polymerization of propylene is carried out in the first stage and the copolymerization of propylene and ethylene is carried out in the second stage in a continuous process. Compared to batch-processed products, low-temperature brittleness and impact resistance are poorer, elongation at break is lower, and the molded product suffers from fish eyes. The following are considered to be the main reasons why such problems occur in the continuous method.
When two or more reactors are connected in series and polymerization is carried out in a continuous manner, each reactor is considered to be in an almost completely mixed state, and therefore the catalyst or the polymer containing the catalyst remains in each reactor. A distribution occurs in time. Catalysts with short residence times produce polymers with a small amount of polymer produced per unit amount of catalyst (hereinafter referred to as catalyst efficiency), and conversely, catalysts with long residence times produce polymers with high catalytic efficiency. . In each reactor, polymers ranging in catalytic efficiency from low to high are produced, and as a result, the composition of all produced polymers has a distribution. The proportion of propylene and ethylene copolymer (hereinafter sometimes referred to as EPR) produced in the second step is, for example, 15%.
Even if the average residence time of each reactor is set so that the EPR
From polymer particles whose fraction is extremely close to 0%,
Up to nearly 100% polymer particles will be included. Among these, it is thought that polymer particles with a relatively large fraction of EPR are not dispersed in the propylene homopolymer, causing fish eyes to occur in the molded product, resulting in deterioration of low-temperature brittleness, impact resistance, etc. Various methods have been proposed to solve these problems in continuous polymerization. Japanese Patent Publication No. 53-25585 and Japanese Patent Application Laid-Open No. 49-53990 propose a method using a large number of reaction vessels. This method yields a block copolymer with physical properties close to those obtained by the batch method, but as the number of tanks increases, the construction cost increases, which is not only economically disadvantageous, but also requires the use of multiple tanks. As a result, product quality control becomes difficult and it is necessary to reduce the number of tanks as much as possible. Japanese Patent Publication Nos. 44-19542 and 55-115417 propose a method in which an electron-donating compound is added during the second stage of propylene-ethylene copolymerization. However, according to studies conducted by the present inventors, this method cannot be said to be sufficiently effective. JP-A-49-61278 proposes a method for lowering the molecular weight of the propylene-ethylene copolymer in the second step. However, according to studies conducted by the present inventors, this method resulted in a decrease in the impact resistance of the molded product. The present inventors conducted various studies to solve the above-mentioned problems, and as a result, the problems were significantly improved by adding a specific aluminum compound during the second stage of propylene-ethylene copolymerization. We discovered what we could do and arrived at the present invention. That is, the present invention provides a titanium-containing solid catalyst component and a compound having the general formula AlR 1 n Cl 3-n (wherein R 1 represents a hydrocarbon group having 1 to 20 carbon atoms, and m represents a number of 3≧m>1.5). ), and in the first step, propylene alone or propylene and ethylene are mixed in a gas phase at a concentration of propylene relative to the sum of propylene and ethylene.
Propylene homopolymer or propylene-ethylene copolymer is produced by polymerizing under conditions of 90 mol% or more, and in the presence of the catalyst system and the polymer produced in the first stage in the second stage. When propylene and ethylene are mixed in the gas phase, the propylene concentration relative to the sum of propylene and ethylene is 90 mol%.
In the method for continuously producing a propylene - ethylene block copolymer by copolymerization under conditions of less than o (in the formula, R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number of 1.5≧n≧0) is newly added and polymerized. A method for producing a propylene-ethylene block copolymer is provided. Although it is not clear why the above-mentioned improvement effect is achieved by adding a specific aluminum compound to the second step in the method of the present invention, the decay of the propylene-ethylene copolymerization rate with respect to time in the second step is This is thought to be due to the fact that the amount of polymer particles with a relatively large EPR fraction was drastically reduced due to the expansion (strengthening) caused by the addition of EPR. Such an effect is brought about by increasing the decay of the copolymerization rate with respect to time, and as will be shown later in a comparative example, adding a substance that poisons the catalyst system, such as an electron-donating compound, In some cases, the copolymerization rate itself is reduced without changing the time decay of the copolymerization rate, or when an activator such as trialkyl aluminum is added to reduce the copolymerization rate decay with time. The same effect as in the method of the present invention is not observed. To further explain the invention in detail, the catalyst system used in the invention is obtained from a titanium-containing solid catalyst component and an organoaluminum compound. As the titanium-containing solid catalyst component, a known carrier-supported catalyst component obtained by contacting a solid magnesium compound, titanium tetrahalide, and an electron-donating compound can also be used, but preferably titanium trichloride is the main component. That is. The solid catalyst component containing titanium trichloride as a main component can be prepared by reducing titanium tetrachloride with metallic aluminum, hydrogen or an organoaluminum compound, or by grinding these, and by contacting or treating these with an electron-donating compound. Although pulverized products can also be used, it is particularly preferable that the aluminum content is 0.15 or less, preferably 0.1 or less, and more preferably 0.02 in terms of the atomic ratio of aluminum to titanium.
and contains a complexing agent.
The content of the complexing agent is 0.001 or more, preferably 0.01 or more in molar ratio of the complexing agent to titanium trichloride in the solid titanium trichloride-based catalyst complex. Specifically, titanium trichloride, a formula with an atomic ratio of aluminum to titanium of titanium trichloride of 0.15 or less
Aluminum halide and trichloride represented by AlR 3 p Those containing a complexing agent in a molar ratio of 0.001 or more to titanium, such as those with the formula TiCl 3 (AlR 3 p X 3-p ) s
(C) t (In the formula, R 3 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, p is a number of 0≦p≦2, C is a complexing agent, and s is a number of 0.15 or less, and t is a number of 0.001 or more), but of course, the three components of TiCl,
In addition to the AlR 3 p It may also contain inorganic solids, olefin polymer powders such as polyethylene, polypropylene, etc. Examples of the complexing agent C include ethers, thioethers, ketones, carboxylic acid esters, amines, carboxylic acid amides, and polysiloxanes, among which ethers and thioethers are particularly preferred. As the ether or thioether, the general formula R 4 -O-R 5 or
Examples include those represented by R 4 -S-R 5 (wherein R 4 and R 5 represent a hydrocarbon group having 15 or less carbon atoms). Examples of AlR 3 p X 3-p include AlCl 3 and AlR 3 Cl 2 . However, such a solid titanium trichloride-based catalyst complex can be prepared by:
Precipitate at the following temperature (b) Easily produce solid titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound or metal aluminum by a method such as treatment with a complexing agent and treatment with a halogen compound. Can be done.
Methods (a) and (b) above have already been proposed in Japanese Patent Publication No. 55-8451.
No. 55-8452, No. 53-24194, No. 55-8003,
No. 54-41040, No. 54-28316, JP-A-53-
It is known in Japanese Patent Publications No. 12796, No. 52-91794, No. 55-116626, Japanese Patent Publication No. 3356-1983, No. 52-40348, etc. Furthermore, in addition to methods (a) and (b),
As described in No. 27871, solid titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound has a molar ratio to the titanium trichloride.
Those prepared by adding 0.5 to 5 ether compounds, heating to 50 to 120°C, and then separating the solid may also be used. On the other hand, the organoaluminum compound used as a cocatalyst in the first and second stages has the general formula AlR 1 n Cl 3-n (wherein R 1 represents a hydrocarbon group having 1 to 20 carbon atoms, m is a number of 3≧m>1.5). When the titanium-containing solid catalyst component is a carrier-supported catalyst component containing a solid magnesium compound, it is preferable to use AlR 1 3 or a mixture of AlR 1 3 and AlR 1 2 Cl. On the other hand, when the catalyst component is mainly TiCl 3 , it is preferable to use AlR 1 2 Cl. In this case, diethylaluminum monochloride in which R 1 is an ethyl group and m is 2 can also be used, but those in which R 1 is a normal propyl group or a normal hexyl group are particularly preferred. The aluminum compound newly added in the second step increases the decay of the copolymerization rate with respect to time, and has the general formula AlR 2 o X 3-o (where R 3 is a carbon number of 1
~20 hydrocarbon groups, X represents a halogen atom, preferably chlorine, and n represents a number of 1.5≧n≧0. Among these, AlR 2 1 . 5 Cl 1 . 5 ,
Preference is given to using AlR 2 Cl 2 or mixtures thereof. Specifically, such compounds include
Examples include those in which R 2 is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Particularly preferred are ethylaluminum dichloride (AlEtCl 2 ), ethylaluminum sesquichloride (AlEt 1.5 Cl 1.5 ), and mixtures thereof because of their ease of availability and handling . AlCl 3 can also be used. The ratio of each catalyst component used is usually a molar ratio of Ti:AlR 1 n Cl 3-n in the titanium-containing solid catalyst component of 1:
From the range of 1 to 100, preferably 1:2 to 40,
The molar ratio of AlR 1 n Cl 3-n :AlR 2 o X 3-o is 1:0.01~
0.50, preferably 1: selected from the range of 0.03 to 0.30. Furthermore, in the method of the present invention, in addition to the above catalyst and cocatalyst, known electron-donating compounds such as carboxylic acid esters, phosphite esters, and amines may be used as the third catalyst component. When the third component is used, the molar ratio of Ti to the third component is selected to be 1:0.01 to 10, preferably 1:0.05 to 2. The titanium-containing solid catalyst component used as a catalyst may be used in the polymerization as it is, but it is preferably pretreated with a small amount of olefin such as propylene or ethylene in the presence of an organoaluminum compound before use. This pretreatment is effective in improving the physical properties of the polymer slurry, such as bulk density. Pretreatment is performed at a temperature lower than the polymerization temperature, generally from 20℃
At 60°C, polymer generated by pretreatment/solid catalyst component = 0.1 to 50/1 (weight ratio), usually 1 to 20/1
It is done as follows. In the method of the present invention, the polymerization is carried out in two stages in the method for producing a propylene-ethylene block copolymer using a catalyst system mainly composed of a titanium-containing solid catalyst component and an organoaluminum compound as described above. However, the polymerization may be carried out in an inert hydrocarbon diluent such as propane, butane, hexane, heptane, benzene, toluene, or in a liquefied propylene diluent. It may also be carried out by so-called gas phase polymerization. First, in the first step, at least a titanium-containing solid catalyst component and an organoaluminum compound represented by the general formula AlR 1 n Cl 3-n are used to homopolymerize propylene or to combine propylene and ethylene in a gas phase. Copolymerization is carried out under conditions where the concentration (concentration of propylene relative to the sum of propylene and ethylene) is 90 mol% or more (hereinafter sometimes simply referred to as propylene homopolymerization). Usually, the polymerization temperature and time are selected so that the amount of propylene homopolymer is 70 to 95% by weight of the total polymer produced.
Polymerization temperature is usually 40-100℃, preferably 50-80℃
selected from the range. The polymerization temperature and the amount of the molecular weight regulator are selected so that the propylene homopolymer obtained in the first step has a melt flow index (hereinafter abbreviated as MFI) of 1 to 150. Examples of the molecular weight modifier include hydrogen, dialkylzinc, etc., but hydrogen is preferred. Usually, the hydrogen concentration in the gas phase (concentration of hydrogen relative to the sum of propylene and ethylene) is about 1 to 30 mol%. Next, in the second step, the propylene homopolymer produced in the first step and the newly added general formula
Propylene and ethylene are copolymerized in the presence of an aluminum compound represented by AlR 2 o X 3-o . The propylene concentration in the gas phase may be less than 90 mol%, but preferably the gas phase propylene concentration is 50 to 85 mol%. This range is the condition in which the amount of by-product of the amorphous polymer is maximized, but it is also the condition in which the impact strength of the final polymer is improved the most. usually,
The polymerization temperature and time are selected such that the amount of propylene-ethylene copolymer is 5 to 30% by weight of the total polymer production. If this amount is less than 5% by weight, the effect of improving impact strength etc. will be small, and if it exceeds 30% by weight, bulk density and free flow properties will deteriorate, which is not preferable. Polymerization temperature is usually 25-70℃, preferably 25-65℃
Selected from the range of °C. If the temperature exceeds 70°C, the resulting propylene-ethylene block copolymer will have poor free flow properties and agglomeration between polymer particles will occur, which is undesirable. Propylene-ethylene copolymer
The polymerization temperature and the amount of hydrogen, which is a molecular weight regulator, are usually selected so that MFI is 0.1 or less. The hydrogen concentration in the gas phase is usually 0.5 to 30 mol%. MFI
If it exceeds 0.1, the improvement in impact strength will be insufficient.
Furthermore, when the MFI is extremely small, for example, when it is less than 10 -7 , the impact strength is greatly improved, but the balancing effect during injection molding becomes large and the dimensional stability deteriorates, which is not preferable. The ethylene content in the total polymer is preferably 2 to 30% by weight. In the case of a continuous system, a separate polymerization tank is used for each stage, and the first stage polymerization tank and the second stage polymerization tank are connected in series. Of course, in each stage, there may be a plurality of polymerization tanks; for example, the first stage polymerization may be carried out in two polymerization tanks connected in series. Transfer of the polymer slurry between polymerization vessels is conveniently carried out in accordance with conventional methods, for example by pressure differential or by means of a slurry pump. Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, the meanings of the abbreviations in the examples and various measurement methods are as follows. Melt flow index MFI (g/10min)
According to ASTM D1238−70, 230℃, load 2.16Kg
It shows the amount of polymer extruded when . First yield strength YS (Kg/cm 2 ) and elongation at break UE
(%) was determined in accordance with ASTM D638-72 by a tensile test of a damper piece punched from a 1 mm thick press sheet. Unless otherwise specified, values are measured at 20°C. Izotsu impact strength (Kg-cm/cm)
was measured using ASTM D256 on a strip cut out from a 5 mm thick press sheet with a notch. Unless otherwise specified, values are at 20°C. The embrittlement temperature Tb (°C) was measured using a test piece punched from a 2 mm thick flat plate according to ASTM D746. In order to evaluate the fixation eyes, a press sheet with a thickness of 1 mm was bent, the amount of fixation eyes was observed, and the results were classified into the following four ranks.
【表】
触媒製造例 １
(A) 固体三塩化チタン系触媒錯体の製造
充分に窒素置換した容量10のオートクレーブ
にｎ−ヘキサン5.0及び四塩化チタン3.0モルを
仕込み、更にジ−ｎ−オクチルエーテル2.7モル
を添加した。これを撹拌下に25℃に保持しつつ、
ジエチルアルミニウムモノクロリド1.0モルをｎ
−ヘキサン0.5に溶解したものを徐々に滴下し
たところ、緑色を帯びた黒褐色の三塩化チタンの
ｎ−ヘキサン均一溶液が得られた。ついで三塩化
チタンの均一溶液を95℃に昇温したところ、昇温
途中より紫色の三塩化チタンの沈澱生成が認めら
れた。95℃で１時間撹拌後、沈澱を別し、ｎ−
ヘキサンで繰返し洗浄して微粒状紫色の固体三塩
化チタン系触媒錯体を得た。元素分析したとこ
ろ、この触媒錯体は式TiCl3（AlCl3）0.003〔（ｎ−
C8H17）2O〕0.11の組成を有していた。
(B) プロピレンによる前処理
充分に窒素置換した容量20のオートクレーブ
にｎ−ヘキサン12.5を仕込み、撹拌下にジ−ｎ
−プロピルアルミニウムモノクロライド1.6モル
及び上記(A)で得た固体三塩化チタン系触媒錯体を
TiCl3の量が250ｇとなるように仕込んだ。つい
で内温を30℃に調節し、撹拌下プロピレンガスの
吹き込みを開始して、重合したプロピレンが1250
ｇになるまで同温度でプロピレンガスの吹き込み
を続けた。ついで固体を分離し、ｎ−ヘキサンで
洗浄を繰返し、ポリプロピレン含有三塩化チタン
を得た。
触媒製造例 ２
(A) 固体三塩化チタン系触媒錯体の製造
充分に窒素置換した容量10のオートクレーブ
に、ｎ−ヘキサン1.0、四塩化チタン2.0モルを
加え、５℃に冷却後、撹拌下にｎ−ヘキサン2.0
とエチルアルミニウムセスキクロライド4.0モ
ルとから成る溶液を30分にわたり滴下した。滴下
終了後、さらに５℃で２時間撹拌を続け熟成を行
つた。ついでｎ−ヘキサンで繰返し洗浄を行い、
赤紫色の固体物質を得た。ｎ−ヘキサン量を3.0
としジイソアミルエーテル0.42を加え、30℃
で１時間撹拌下に反応を行つた。ついでｎ−ヘキ
サンで繰返し洗浄を行い、減圧乾燥を行つて褐色
の物質を得た。ついで８モルの四塩化チタンを加
えた。35℃で1.5時間反応を行つた後ｎ−ヘキサ
ンで繰返し洗浄を行つて紫色の固体三塩化チタン
系触媒錯体を得た。元素分析したところ、式
TiCl3・（AlCl3）0.01〔（ｉ−C5H11）2O〕0.11
の組成を有していた。
(B) プロピレンによる前処理
上記(A)で得た固体三塩化チタン系触媒錯体に対
し、触媒製造例１(B)と同様にしてプロピレンによ
る前処理を行つた。
実施例 １
容量170、70及び60の撹拌機付反応槽を
この順に直列に連結して２段階からなる連続重合
を行つた。第１及び第２の反応槽ではプロピレン
の単独重合を、第３の反応槽ではプロピレンとエ
チレンの共重合を行つた。まず第１の反応槽に液
化プロピレン、水素を気相の水素濃度が5.5モル
％になる量、触媒製造例１(B)で得た三塩化チタ
ン、ジ−ｎ−プロピルアルミニウムモノクロライ
ド（DPAと略す）をTiCl3に対するモル比で８に
なる量、酢酸フエニルをTiCl3に対するモル比で
0.13になる量、供給した。この第１反応槽におけ
る重合温度は70℃であり、平均滞留時間（重合時
間）は4.5時間であつた。この第１反応槽からの
流出物をそのまま第２反応槽に供給し、追加の液
化プロピレン及び水素を気相の水素濃度が６モル
％になる量連続的に供給した、この第２反応槽に
おける重合温度は67℃であり、平均滞留時間（重
合時間）は1.6時間であつた。この第２反応槽か
らの流出物をそのまま第３反応槽に供給し、液化
プロピレン及びエチレンを気相のプロピレン濃度
が65モル％になる量連続的に供給した。気相の水
素濃度は３モル％になる様に調節した。さらにエ
チルアルミニウムダイクロライド（AlEtCl2）
を、AlEtCl2／DPAモル比が0.08になるように供
給した。この第３反応槽における重合温度は45℃
であり、平均滞留時間（重合時間）は1.5時間で
あつた。第３反応槽からの流出物をフラツシユし
未反応プロピレンをパージした後、重合で得られ
たポリマーを全て重合体粉末として回収しプロピ
レンオキシドガスで120℃で連続的に処理を行つ
た。以上のようにして得た製品粉末を添加剤とし
てBHT.（２，６−ジ−ｔ−ブチル−ｐ−クレゾ
ール）を0.1％、イルガノツクス1010（ガイギ−社
安定剤、商標）を0.1％、ジラウリルチオジプロ
ピオネートを0.2％、ステアリン酸カルシウムを
0.2％添加し、内径40mmの単軸押出機を用いて220
℃で混練を行つた。ついでプレスシートを成形
し、各種物性を測定した。その結果、フイツシ
ユ・アイ評価は◎、即ちフイツシユ・アイは殆ん
ど認められなかつた。MFIは2.3であり、脆化温
度Tbは23.2℃、破断点伸度UEは762％、第１降
伏強度YSは265Kg／cm2、アイゾツト衝撃強度は
11.5Kg・cm／cmであつた。
実施例 ２〜９
実施例１と全く同一の条件で第１反応槽及び第
２反応槽でプロピレンの単独重合を行つた。つい
で第３反応槽でプロピレンとエチレンの共重合を
行う際、表１に示すような種類及び量のアルミニ
ウム化合物を供給した。また第３反応槽における
重合量を合せる為に第３反応槽における重合条件
を表１に示すように変更した。それ以外は実施例
１と同様にして重合及び混練を行つてプレスシー
トを成形し各種物性を測定した。その結果を表１
に示した。
比較例 １〜４
実施例１と全く同一の条件で第１反応槽及び第
２反応槽でプロピレンの単独重合を行つた。つい
で第３反応槽でプロピレンとエチレンの共重合を
行う際、比較例１においては何も添加せず、比較
例２においてはトリエチルアルミニウム
（AlEt3）を、比較例３においてはメチルメタク
リレート（MMA）を、比較例４においてはエタ
ノール（EtOH）をそれぞれ表２に示すような量
となるように供給した。また、第３反応槽におけ
る重合量を合わせる為に第３反応槽における重合
条件を表２に示すように変更した。それ以外は実
施例１と同様にして重合及び混練を行つてプレス
シートを成形し、各種物性を測定した。その結果
を表２に示した。
以上の実施例及び比較例よりプロピレン−エチ
レン共重合時に特定のアルミニウム化合物を添加
する本発明方法に従えば、フイツシユ・アイが少
く、脆化温度が低く即ち低温脆性が改良された、
破断点伸度も充分に大きく、耐衝撃性も充分に大
きい成形品を与えるブロツク共重合体が得られる
ことが明らかである。[Table] Catalyst production example 1 (A) Production of solid titanium trichloride-based catalyst complex A 10-capacity autoclave that was sufficiently purged with nitrogen was charged with 5.0 moles of n-hexane and 3.0 moles of titanium tetrachloride, and further 2.7 moles of di-n-octyl ether. mol was added. While stirring this and keeping it at 25℃,
1.0 mol of diethylaluminium monochloride n
- When a solution dissolved in 0.5 hexane was gradually added dropwise, a homogeneous solution of titanium trichloride in n-hexane was obtained, which was dark brown with a green tinge. Then, when the homogeneous solution of titanium trichloride was heated to 95°C, a purple precipitate of titanium trichloride was observed to form during the temperature rise. After stirring at 95℃ for 1 hour, the precipitate was separated and n-
After repeated washing with hexane, a finely divided purple solid titanium trichloride catalyst complex was obtained. Elemental analysis reveals that the catalyst complex has the formula TiCl 3 (AlCl 3 )0.003 [(n-
It had a composition of C 8 H 17 ) 2 O]0.11. (B) Pretreatment with propylene Charge 12.5 liters of n-hexane into an autoclave with a capacity of 20 that has been sufficiently purged with nitrogen, and add 12.5 ml of n-hexane to a
- 1.6 mol of propylaluminum monochloride and the solid titanium trichloride catalyst complex obtained in (A) above.
TiCl 3 was charged in an amount of 250 g. Next, the internal temperature was adjusted to 30°C, and propylene gas was started to be blown while stirring, until the polymerized propylene reached 1250°C.
Propylene gas was continued to be blown at the same temperature until the temperature reached 100 g. The solid was then separated and washed repeatedly with n-hexane to obtain polypropylene-containing titanium trichloride. Catalyst production example 2 (A) Production of solid titanium trichloride-based catalyst complex Into a 10 capacity autoclave that was sufficiently purged with nitrogen, 1.0 mol of n-hexane and 2.0 mol of titanium tetrachloride were added, and after cooling to 5°C, the mixture was heated with n-hexane while stirring. −Hexane 2.0
and 4.0 mol of ethylaluminum sesquichloride was added dropwise over 30 minutes. After completion of the dropwise addition, stirring was continued for an additional 2 hours at 5°C for ripening. Then, wash repeatedly with n-hexane,
A reddish-purple solid material was obtained. The amount of n-hexane is 3.0
Add 0.42% of diisoamyl ether and heat at 30°C.
The reaction was carried out under stirring for 1 hour. The mixture was then washed repeatedly with n-hexane and dried under reduced pressure to obtain a brown substance. Then 8 moles of titanium tetrachloride were added. After carrying out the reaction at 35°C for 1.5 hours, the reaction mixture was washed repeatedly with n-hexane to obtain a purple solid titanium trichloride catalyst complex. As a result of elemental analysis, it had a composition of the formula TiCl3 .( AlCl3 ) 0.01 [(i- C5H11 ) 2O ]0.11. (B) Pretreatment with propylene The solid titanium trichloride catalyst complex obtained in (A) above was pretreated with propylene in the same manner as in Catalyst Production Example 1 (B). Example 1 Continuous polymerization consisting of two stages was carried out by connecting reactors equipped with stirrers with capacities of 170, 70 and 60 in series in this order. Homopolymerization of propylene was carried out in the first and second reaction vessels, and copolymerization of propylene and ethylene was carried out in the third reaction vessel. First, in the first reaction tank, liquefied propylene, hydrogen were added in an amount such that the hydrogen concentration in the gas phase was 5.5 mol%, titanium trichloride obtained in catalyst production example 1 (B), di-n-propyl aluminum monochloride (DPA) and omitted) in a molar ratio of 8 to TiCl3 , and phenyl acetate in a molar ratio of TiCl3 to 8.
I supplied the amount to be 0.13. The polymerization temperature in this first reaction tank was 70°C, and the average residence time (polymerization time) was 4.5 hours. In this second reaction tank, the effluent from the first reaction tank was directly supplied to the second reaction tank, and additional liquefied propylene and hydrogen were continuously supplied in an amount such that the hydrogen concentration in the gas phase was 6 mol%. The polymerization temperature was 67°C, and the average residence time (polymerization time) was 1.6 hours. The effluent from the second reaction tank was directly supplied to the third reaction tank, and liquefied propylene and ethylene were continuously supplied in an amount such that the propylene concentration in the gas phase was 65 mol%. The hydrogen concentration in the gas phase was adjusted to 3 mol%. Furthermore, ethylaluminum dichloride (AlEtCl 2 )
were supplied so that the AlEtCl 2 /DPA molar ratio was 0.08. The polymerization temperature in this third reaction tank is 45℃
The average residence time (polymerization time) was 1.5 hours. After flushing the effluent from the third reaction tank and purging unreacted propylene, all the polymer obtained by polymerization was recovered as a polymer powder and continuously treated with propylene oxide gas at 120°C. The product powder obtained as described above was used as additives, including 0.1% BHT. 0.2% lauryl thiodipropionate, calcium stearate
220 using a single screw extruder with an inner diameter of 40 mm, adding 0.2%
Kneading was carried out at ℃. A press sheet was then formed and various physical properties were measured. As a result, the fish eyes were evaluated as ◎, that is, almost no fish eyes were observed. MFI is 2.3, embrittlement temperature Tb is 23.2℃, elongation at break UE is 762%, first yield strength YS is 265Kg/cm 2 , Izotsu impact strength is
It was 11.5Kg・cm/cm. Examples 2 to 9 Propylene homopolymerization was carried out in the first reaction tank and the second reaction tank under exactly the same conditions as in Example 1. Then, when copolymerizing propylene and ethylene in the third reaction tank, aluminum compounds of the type and amount shown in Table 1 were supplied. Furthermore, in order to match the amount of polymerization in the third reaction tank, the polymerization conditions in the third reaction tank were changed as shown in Table 1. Other than that, polymerization and kneading were carried out in the same manner as in Example 1, a press sheet was formed, and various physical properties were measured. Table 1 shows the results.
It was shown to. Comparative Examples 1 to 4 Propylene homopolymerization was carried out in the first reaction tank and the second reaction tank under exactly the same conditions as in Example 1. Then, when copolymerizing propylene and ethylene in the third reaction tank, nothing was added in Comparative Example 1, triethylaluminum (AlEt 3 ) was added in Comparative Example 2, and methyl methacrylate (MMA) was added in Comparative Example 3. In Comparative Example 4, ethanol (EtOH) was supplied in the amounts shown in Table 2. Furthermore, in order to match the amount of polymerization in the third reaction tank, the polymerization conditions in the third reaction tank were changed as shown in Table 2. Other than that, polymerization and kneading were performed in the same manner as in Example 1 to form a press sheet, and various physical properties were measured. The results are shown in Table 2. From the above Examples and Comparative Examples, if the method of the present invention was followed in which a specific aluminum compound was added during propylene-ethylene copolymerization, there were fewer fish eyes and the embrittlement temperature was lower, that is, the low-temperature brittleness was improved.
It is clear that a block copolymer can be obtained which gives molded articles with sufficiently high elongation at break and sufficiently high impact resistance.
【表】【table】
【表】【table】
【表】
実施例10〜14及び比較例５，６
実施例１と同様の撹拌機付反応槽を用いて２段
階からなる連続重合を行つた。第１及び第２の反
応槽ではプロピレンの単独重合を、第３の反応槽
ではプロピレンとエチレンの共重合を行つた。ま
ず第１の反応槽に液化プロピレン、水素を気相の
水素濃度が5.5モル％になる量、触媒製造例２(B)
で得た三塩化チタン、ジエチルアルミニウムモノ
クロライドをTiCl3に対するモル比で８になる
量、酢酸フエニルをTiCl4に対するモル比で0.2に
なる量、供給した。この第１反応槽における重合
温度は70℃であり、平均滞留時間（重合時間）は
4.5時間であつた。この第１反応槽からの流出物
はそのまま第２反応槽に供給し、追加の液化プロ
ピレン及び水素を気相の水素濃度が６モル％にな
る量連続的に供給した。この第２反応槽における
重合温度は67℃であり、平均滞留時間（重合時
間）は1.6時間であつた。この第２反応槽からの
流出物をそのまま第３反応槽に供給し、液化プロ
ピレン及びエチレンを気相のプロピレン濃度が65
モル％になる量連続的に供給した。気相の水素濃
度は３モル％になる様に調節した。さらに表３に
示す種類と量のアルミニウム化合物を連続的に供
給した。但し比較例５では何も添加せず、比較例
６ではトリエチルアルミニウムを添加した。その
他、第３反応槽における重合条件は表３に示す。
第３反応槽からの流出物をフラツシユし未反応プ
ロピレンをパージした後、重合体粉末をプロピレ
ンオキシドガスで120℃で連続的に処理を行つた。
以上のようにして得た製品粉末に添加剤として商
品名“BHT”を0.1％、“Irganox1010”を0.1％、
ジラウリルチオジプロピオネートを0.2％、ステ
アリン酸カルシウムを0.2％添加し、内径40mmの
単軸押出機を用いて220℃で混練を行つた。つい
でプレスシートを成形し、各種物性を測定した。
その結果を表３に示した。本発明方法によるとフ
イツシユ・アイ、脆化温度Tb、破断点伸度UE及
びアイゾツト衝撃強度が大巾に改良されることが
明らかである。[Table] Examples 10 to 14 and Comparative Examples 5 and 6 Using the same reactor equipped with a stirrer as in Example 1, continuous polymerization was carried out in two stages. Homopolymerization of propylene was carried out in the first and second reaction vessels, and copolymerization of propylene and ethylene was carried out in the third reaction vessel. First, liquefied propylene and hydrogen were placed in the first reaction tank in an amount such that the hydrogen concentration in the gas phase was 5.5 mol%. Catalyst Production Example 2 (B)
Titanium trichloride and diethylaluminium monochloride obtained in step 1 were supplied in an amount having a molar ratio of 8 to TiCl 3 , and phenyl acetate was supplied in an amount having a molar ratio of 0.2 to TiCl 4 . The polymerization temperature in this first reaction tank is 70℃, and the average residence time (polymerization time) is
It took 4.5 hours. The effluent from the first reaction tank was directly supplied to the second reaction tank, and additional liquefied propylene and hydrogen were continuously supplied in an amount such that the hydrogen concentration in the gas phase was 6 mol %. The polymerization temperature in this second reaction tank was 67°C, and the average residence time (polymerization time) was 1.6 hours. The effluent from this second reaction tank is supplied as it is to the third reaction tank, and liquefied propylene and ethylene are added until the propylene concentration in the gas phase is 65.
It was continuously fed in an amount of mol %. The hydrogen concentration in the gas phase was adjusted to 3 mol%. Furthermore, aluminum compounds of the type and amount shown in Table 3 were continuously supplied. However, in Comparative Example 5, nothing was added, and in Comparative Example 6, triethylaluminum was added. Other polymerization conditions in the third reaction tank are shown in Table 3.
After flushing the effluent from the third reactor and purging unreacted propylene, the polymer powder was continuously treated with propylene oxide gas at 120°C.
As additives to the product powder obtained as above, 0.1% of the product name "BHT" and 0.1% of "Irganox1010" were added.
0.2% dilauryl thiodipropionate and 0.2% calcium stearate were added and kneaded at 220°C using a single screw extruder with an inner diameter of 40 mm. A press sheet was then formed and various physical properties were measured.
The results are shown in Table 3. It is clear that the method of the present invention significantly improves the fish eye, the embrittlement temperature Tb, the elongation at break UE, and the isot impact strength.
【表】【table】
【表】
比較例 ７，８
容量170、70、５及び60の撹拌機付反
応槽をこの順に直列に連結して２段階からなる連
続重合を行つた。容量170及び70の第１及び
第２の反応槽では第１段階としてのプロピレン単
独重合を実施例１におけるプロピレン単独重合と
全く同様にして行つた。ついで第２反応槽からの
流出物をそのまま容量５の処理槽に供給し、さ
らにAlEtCl2をAlEtCl2／DPAモル比が比較例７
では0.08、比較例８では0.16になるように供給し
た。この処理槽における処理温度は67℃、平均滞
留時間（処理時間）は５分であつた。処理槽から
の流出物をそのまま容量60の第３反応槽に供給
し、液化プロピレン及びエチレンを連続的に供給
し第２段階としてのプロピレン−エチレン共重合
を行つた。気相のプロピレン濃度、水素濃度及び
重合温度は実施例１におけるプロピレン−エチレ
ン共重合の場合と同様に各々、65モル％、３モル
％及び45℃に保つた。但し平均滞留時間（重合時
間）は表４に示すように変更した。ついで第３反
応槽からの流出物をフラツシユした後、実施例１
と同様の処理及び混練を行い、各種物性を測定し
た。その結果を表４に示した。
AlEtCl2を第３反応槽、即ち第２段階のプロピ
レンとエチレンの共重合時に添加する実施例に比
べ、AlEtCl2をあらかじめ共触媒であるDPAと接
触、反応させた後に第３反応槽、即ち第２段階の
プロピレンとエチレンの共重合時に添加する比較
例７，８ではフイツシユ・アイ評価、脆化温度等
が不良であり、AlEtCl2を添加することの効果が
認められなかつた。さらに比較例８ではプロピレ
ン−エチレン共重合体の量が目標の13〜14％に達
しなかつた。
これは比較例７，８の如き方法では、第２段階
における共重合速度そのものを小さくするだけで
共重合速度の対時間減衰を拡大（強化）するもの
ではない為に本発明方法の如き効果が認められな
かつたものと考えられる。いずれにせよ、本発明
方法では一般式AlR2 oX3-oで表わされるアルミニ
ウム化合物を共触媒と前もつて接触、反応させる
ことなく第２段階の共重合時に添加することが重
要である。[Table] Comparative Examples 7 and 8 Continuous polymerization consisting of two stages was carried out by connecting reactors with stirrers with capacities of 170, 70, 5 and 60 in series in this order. In the first and second reactors having capacities of 170 and 70, the first stage of propylene homopolymerization was carried out in exactly the same manner as the propylene homopolymerization in Example 1. Next, the effluent from the second reaction tank was directly supplied to a treatment tank with a capacity of 5, and AlEtCl 2 was further added to the AlEtCl 2 /DPA molar ratio of Comparative Example 7.
In Comparative Example 8, the amount was 0.08, and in Comparative Example 8, it was 0.16. The treatment temperature in this treatment tank was 67°C, and the average residence time (treatment time) was 5 minutes. The effluent from the treatment tank was directly fed to a third reaction tank with a capacity of 60, and liquefied propylene and ethylene were continuously fed to carry out the second stage of propylene-ethylene copolymerization. The propylene concentration, hydrogen concentration, and polymerization temperature in the gas phase were maintained at 65 mol%, 3 mol%, and 45°C, respectively, as in the propylene-ethylene copolymerization in Example 1. However, the average residence time (polymerization time) was changed as shown in Table 4. Then, after flashing the effluent from the third reaction tank, Example 1
The same treatment and kneading as above were performed, and various physical properties were measured. The results are shown in Table 4. Compared to the example in which AlEtCl 2 is added in the third reaction tank, that is, during the second stage of copolymerization of propylene and ethylene, AlEtCl 2 is added in advance by contacting and reacting with DPA, which is a cocatalyst, and then added in the third reaction tank, that is, during the copolymerization of propylene and ethylene. In Comparative Examples 7 and 8, in which AlEtCl 2 was added during the two-stage copolymerization of propylene and ethylene, the fish eye evaluation, embrittlement temperature, etc. were poor, and the effect of adding AlEtCl 2 was not recognized. Furthermore, in Comparative Example 8, the amount of propylene-ethylene copolymer did not reach the target of 13 to 14%. This is because methods such as Comparative Examples 7 and 8 only reduce the copolymerization rate itself in the second stage, but do not expand (strengthen) the decay of the copolymerization rate over time, and therefore do not have the same effect as the method of the present invention. It is thought that this was not approved. In any case, in the method of the present invention, it is important to add the aluminum compound represented by the general formula AlR 2 o
Claims (1)
Cl3-n（式中R1は炭素数１〜20の炭化水素基を表
わし、ｍは３≧ｍ＞1.5の数を示す）で表わされ
る有機アルミニウム化合物とを主体とする触媒系
を用い、第１段階においてプロピレン単独または
プロピレンとエチレンとを気相中のプロピレン濃
度が90モル％以上である条件下で重合することに
よつてプロピレン単独重合体またはプロピレン−
エチレン共重合体を製造し、第２段階において該
触媒系および第１段階で製造された重合体の存在
下でプロピレンとエチレンとを気相中のプロピレ
ン濃度が90モル％未満である条件下で共重合させ
てプロピレン−エチレンブロツク共重合体を連続
的に製造する方法において、該第２段階に、共重
合速度の対時間減衰を大きくする一般式AlR2 o
X3-o（式中R2は炭素数１〜20の炭化水素基を表わ
し、Ｘはハロゲン原子を表わし、ｎは1.5≧ｎ≧
０の数を示す）で表わされるアルミニウム化合物
をあらたに添加して重合することを特徴とするプ
ロピレン−エチレンブロツク共重合体の製造法。 ２ チタン含有固体触媒成分が三塩化チタン、三
塩化チタンのチタンに対するアルミニウムの原子
比で0.15以下の式AlR3 pX3-p（式中R3は炭素数１
〜20の炭化水素基、Ｘはハロゲン原子、ｐは０≦
ｐ≦２の数である）で表わされるハロゲン化アル
ミニウムおよび三塩化チタンに対しモル比で
0.001以上の錯化剤を含むものである特許請求の
範囲第１項記載のブロツク共重合体の製造法。 ３ チタン含有固体触媒成分が、エーテル又はチ
オエーテルの存在下に液状化した三塩化チタンを
含有する液状物から150℃以下の温度で析出させ
たものである特許請求の範囲第１項に記載のブロ
ツク共重合体の製造法。 ４ チタン含有固体触媒成分が、四塩化チタンを
有機アルミニウム化合物又は金属アルミニウムで
還元して得られた固体三塩化チタンを、錯化剤処
理及びハロゲン化合物処理して得られるものであ
る特許請求の範囲第１項に記載のブロツク共重合
体の製造法。[Claims] 1. Titanium-containing solid catalyst component and general formula AlR 1 n
Using a catalyst system mainly consisting of an organoaluminum compound represented by Cl 3-n (in the formula, R 1 represents a hydrocarbon group having 1 to 20 carbon atoms, and m represents a number of 3≧m>1.5), In the first step, propylene alone or propylene and ethylene are polymerized under conditions where the propylene concentration in the gas phase is 90 mol% or more to produce a propylene homopolymer or propylene-
An ethylene copolymer is produced, and in a second step propylene and ethylene are mixed in the presence of the catalyst system and the polymer produced in the first step under conditions such that the propylene concentration in the gas phase is less than 90 mol%. In the method of continuously producing a propylene-ethylene block copolymer by copolymerization, the second step includes the general formula AlR 2 o which increases the decay of the copolymerization rate with respect to time.
X 3-o (in the formula, R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n is 1.5≧n≧
1. A method for producing a propylene-ethylene block copolymer, which comprises additionally adding and polymerizing an aluminum compound represented by the number 0. 2 The titanium-containing solid catalyst component is titanium trichloride , and the atomic ratio of aluminum to titanium in titanium trichloride is 0.15 or less.
~20 hydrocarbon groups, X is a halogen atom, p is 0≦
p≦2) in molar ratio to aluminum halide and titanium trichloride.
The method for producing a block copolymer according to claim 1, which contains 0.001 or more of a complexing agent. 3. The block according to claim 1, wherein the titanium-containing solid catalyst component is precipitated at a temperature of 150° C. or lower from a liquid material containing titanium trichloride liquefied in the presence of an ether or thioether. Method for producing copolymers. 4 Claims in which the titanium-containing solid catalyst component is obtained by treating solid titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound or metal aluminum by treating it with a complexing agent and a halogen compound. A method for producing a block copolymer according to item 1.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3221681A JPS57147508A (en) | 1981-03-06 | 1981-03-06 | Preparation of propylene-ethylene block copolymer |
| US06/347,425 US4380608A (en) | 1981-03-06 | 1982-02-10 | Process for producing propylene-ethylene block copolymer |
| DE8282101236T DE3271299D1 (en) | 1981-03-06 | 1982-02-18 | Process for producing propylene-ethylene block copolymer |
| EP19820101236 EP0059865B1 (en) | 1981-03-06 | 1982-02-18 | Process for producing propylene-ethylene block copolymer |
| CA000397496A CA1160793A (en) | 1981-03-06 | 1982-03-03 | Process for producing propylene-ethylene block copolymer |
| AU81147/82A AU543422B2 (en) | 1981-03-06 | 1982-03-05 | Propylene-ethylene block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3221681A JPS57147508A (en) | 1981-03-06 | 1981-03-06 | Preparation of propylene-ethylene block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57147508A JPS57147508A (en) | 1982-09-11 |
| JPH0244846B2 true JPH0244846B2 (en) | 1990-10-05 |
Family
ID=12352724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3221681A Granted JPS57147508A (en) | 1981-03-06 | 1981-03-06 | Preparation of propylene-ethylene block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57147508A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3214246A1 (en) * | 1982-04-17 | 1983-10-27 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING PROPYLENE-ETHYLENE-POLYMERISATES OF THE TYPE OF THE SOCIAL "BLOCK-COPOLYMERISATE" |
| JPS6169821A (en) * | 1984-09-14 | 1986-04-10 | Mitsui Petrochem Ind Ltd | Production of block propylene copolymer |
| JP3508187B2 (en) * | 1993-11-10 | 2004-03-22 | チッソ株式会社 | Continuous production of propylene / ethylene block copolymer |
| JP3355864B2 (en) * | 1995-04-24 | 2002-12-09 | チッソ株式会社 | Continuous production of high-rigidity propylene / ethylene block copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329390A (en) * | 1976-09-01 | 1978-03-18 | Toa Nenryo Kogyo Kk | Preparation of ethylene-propylene block copolymer |
| JPS5330686A (en) * | 1976-09-02 | 1978-03-23 | Toa Nenryo Kogyo Kk | Preparation of ethylene-propylene block copolymers |
-
1981
- 1981-03-06 JP JP3221681A patent/JPS57147508A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329390A (en) * | 1976-09-01 | 1978-03-18 | Toa Nenryo Kogyo Kk | Preparation of ethylene-propylene block copolymer |
| JPS5330686A (en) * | 1976-09-02 | 1978-03-23 | Toa Nenryo Kogyo Kk | Preparation of ethylene-propylene block copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57147508A (en) | 1982-09-11 |
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