JPS63241050A - Ultra-high mw ethylene polymer composition and its production - Google Patents
Ultra-high mw ethylene polymer composition and its productionInfo
- Publication number
- JPS63241050A JPS63241050A JP7412187A JP7412187A JPS63241050A JP S63241050 A JPS63241050 A JP S63241050A JP 7412187 A JP7412187 A JP 7412187A JP 7412187 A JP7412187 A JP 7412187A JP S63241050 A JPS63241050 A JP S63241050A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- ultra
- polymerization
- high molecular
- ethylene polymer
- 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.)
- Pending
Links
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 94
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001155 polypropylene Polymers 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 17
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 19
- 239000010936 titanium Substances 0.000 description 19
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- -1 polyethylene Polymers 0.000 description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 238000012685 gas phase polymerization Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000004291 polyenes Chemical class 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VPQUPTMYONRDSS-UHFFFAOYSA-N benzhydryloxy-methoxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)OC(C=1C=CC=CC=1)C1=CC=CC=C1 VPQUPTMYONRDSS-UHFFFAOYSA-N 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性、引張強度、成形加工性が改良され、且
つ、剛性、摺動特性、衝撃強度に優れた超高分子量エチ
レン重合体組成物及びその製法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an ultra-high molecular weight ethylene polymer composition that has improved heat resistance, tensile strength, and moldability, and has excellent rigidity, sliding properties, and impact strength. Concerning products and their manufacturing methods.
超高分子量ポリエチレンは汎用のポリエチレンに比べ、
耐衝撃性、耐摩耗性、耐薬品性、引張強度に優れており
、エンジニアリングプラスチックとしてその用途が拡が
りつつある。しかしながら汎用のポリエチレンに比較し
て溶融粘度が極めて高く流動性が悪いため、従来の押出
成形や射出成形によって成形することは非常に難しく、
その殆どは圧縮成形によって成形されており、一部ロツ
ド等が極く低速で押出成形されているのが現状であった
。Compared to general-purpose polyethylene, ultra-high molecular weight polyethylene
It has excellent impact resistance, abrasion resistance, chemical resistance, and tensile strength, and its use as an engineering plastic is expanding. However, compared to general-purpose polyethylene, it has an extremely high melt viscosity and poor fluidity, making it extremely difficult to mold using conventional extrusion or injection molding.
Most of them are formed by compression molding, and some rods and the like are currently extruded at extremely low speeds.
従来、超高分子量ポリエチレンの溶融成形性を改善する
方法として、超高分子量ポリエチレンに低分子量ないし
高分子量のポリオレフィンを混合する方法が提案されて
いる。特開昭５７−１７７０３６号公報には、分子量１
００万以上の超高分子量ポリエチレン１００重量部と分
子量５ 、０００〜２０，０００の低分子量ポリエチレ
ン１０〜６０重量部とからなる成形性の改良された超高
分子量ポリエチレン組成物が開示されている。同公開公
報には同超高分子量ポリエチレン組成物の成形性は、厚
さ５０ｍｍのスラブを圧縮成形法で成形する場合、超高
分子量ポリエチレンのみでは２００℃×３時間の成形サ
イクルを必要したのに対し２００℃×２時間の成形サイ
クルに改善され、またラム押出成形法ではパイプ押出速
度が同様に５ｃｍ／分からＬＯｃｍ／分に改善されたこ
とが記載されている。Conventionally, as a method for improving the melt moldability of ultra-high molecular weight polyethylene, a method of mixing low-molecular weight to high-molecular weight polyolefin with ultra-high molecular weight polyethylene has been proposed. JP-A-57-177036 discloses that the molecular weight is 1.
An ultra-high molecular weight polyethylene composition with improved moldability is disclosed which comprises 100 parts by weight of ultra-high molecular weight polyethylene having a molecular weight of 5,000,000 or more and 10-60 parts by weight of a low molecular weight polyethylene having a molecular weight of 5.0,000 to 20,000. The publication states that the moldability of the ultra-high molecular weight polyethylene composition is that when molding a slab with a thickness of 50 mm by compression molding, a molding cycle of 200°C x 3 hours was required for ultra-high molecular weight polyethylene alone. On the other hand, it is described that the molding cycle was improved to 200° C. x 2 hours, and that the pipe extrusion speed was similarly improved from 5 cm/min to LO cm/min in the ram extrusion method.
上記超高分子量ポリエチレン組成物の成形性は上記の如
く改善されているが、改質剤として、低分子量ポリエチ
レンを添加するので、超高分子量ポリエチレン本来の特
徴である引張強度等の優れた機械的性質の低下は免れえ
ない。The moldability of the ultra-high molecular weight polyethylene composition has been improved as described above, but since low molecular weight polyethylene is added as a modifier, the ultra-high molecular weight polyethylene composition has excellent mechanical properties such as tensile strength and other characteristics inherent to ultra-high molecular weight polyethylene. A decline in character cannot be avoided.
特開昭５９−１２０６０５号公報には水素存在下でプロ
ピレン又はプロピレンを主成分とするモノマーを重合し
て重合体の２〜６０重量％のポリプロピレンを製造し、
残り一段階以上で実質的に水素の不存在下でエチレン又
はエチレンを主成分とするモノマーを重合して重合体の
９８〜４０重量％の超高分子量ポリエチレン成分を製造
し、成形加工性の改善された超高分子量ポリエチレン系
樹脂の製造方法が開示されている。そして同公開公報に
は、最終重合体の分散の均一性という点からは、ポリプ
ロピレンを重合した後に超高分子量ポリエチレン成分を
重合することが好ましいとも記載されている。JP-A-59-120605 discloses that propylene or a monomer containing propylene as a main component is polymerized in the presence of hydrogen to produce polypropylene of 2 to 60% by weight of the polymer,
In the remaining one or more steps, ethylene or a monomer containing ethylene as a main component is polymerized in the substantial absence of hydrogen to produce an ultra-high molecular weight polyethylene component of 98 to 40% by weight of the polymer, thereby improving moldability. A method for producing an ultra-high molecular weight polyethylene resin is disclosed. The publication also states that from the viewpoint of uniformity of dispersion of the final polymer, it is preferable to polymerize the ultra-high molecular weight polyethylene component after polymerizing polypropylene.
上記方法で得られる超高分子量ポリエチレン系樹脂は超
高分子量ポリエチレンに比べて、成形加工性、剛性は幾
分改良はされるものの、引張強度はむしろ低下し、耐熱
性も改良されないことが分かった。It was found that although the ultra-high molecular weight polyethylene resin obtained by the above method has some improvement in moldability and rigidity compared to ultra-high molecular weight polyethylene, the tensile strength is rather lower and the heat resistance is not improved. .
そこで、本発明者らは引張強度等の機械的強度の低下を
招くことなく、超高分子量エチレン重合体の成形加工性
、耐熱性等を改良すべく種々検討した結果、実質的に水
素の不存在下でエチレン又はエチレンを主成分とするモ
ノマーを重合して超高分子量エチレン重合体を生成させ
、次いでプロピレン又はプロピレンを主成分とするモノ
マーを重合して高分子量プロピレン重合体を生成させる
多段重合法によって製造される超高分子量エチレン重合
体組成物が、従来の超高分子量エチレン重合体組成物に
比べて、更に成形加工性、剛性が改良され、しかも超高
分子量ポリエチレンと比べても、引張強度、耐熱性が優
れていることが分かり、本発明を完成するに至った。Therefore, the present inventors conducted various studies to improve the moldability, heat resistance, etc. of ultra-high molecular weight ethylene polymers without causing a decrease in mechanical strength such as tensile strength. Multi-stage polymerization in which ethylene or an ethylene-based monomer is polymerized in the presence of an ultra-high molecular weight ethylene polymer, and then propylene or a propylene-based monomer is polymerized to produce a high molecular weight propylene polymer. The ultra-high molecular weight ethylene polymer composition produced by the method has improved moldability and rigidity compared to conventional ultra-high molecular weight ethylene polymer compositions, and also has higher tensile strength than ultra-high molecular weight polyethylene. It was found that the material had excellent strength and heat resistance, leading to the completion of the present invention.
すなわち、本発明は、
（１）１３５℃デカリン溶媒中で測定した極限粘度〔η
〕ｅが少なくとも１５ｄｌ／ｇの超高分子量エチレン重
合体（Ａ）と１３５℃デカリン溶媒中で測定した極限粘
度〔η〕ｐが少なくとも５．０ｄｌ／ｇの高分子量プロ
ピレン重合体（Ｂ）とから実質的になり、（ＩＩ）上記
超高分子量エチレン重合体（Ａ）は該超高分子量エチレ
ン重合体（Ａ）と高分子量プロピレン重合体（Ｂ）との
総重量に対し１０〜８５重量％の範囲にあり、
（ＩＩＩ）１３５℃デカリン溶媒中で測定した極限粘度
〔η〕ｃが６．０〜４０ａ／ｇの範囲にあることを特徴
とする特許
合体組成物及びその製法を提供するものである。That is, the present invention provides: (1) Intrinsic viscosity [η
] An ultra-high molecular weight ethylene polymer (A) with an e of at least 15 dl/g and a high molecular weight propylene polymer (B) with an intrinsic viscosity [η] p of at least 5.0 dl/g measured in a decalin solvent at 135°C. (II) The ultra-high molecular weight ethylene polymer (A) contains 10 to 85% by weight based on the total weight of the ultra-high molecular weight ethylene polymer (A) and the high molecular weight propylene polymer (B). (III) A patented composite composition characterized in that the intrinsic viscosity [η]c measured in a decalin solvent at 135° C. is in the range of 6.0 to 40 a/g, and a method for producing the same. be.
〔作 用〕
本発明においていう超高分子量エチレン重合体（Ａ）は
、１３５℃デカリン溶媒中で測定した極限粘度〔η〕ｅ
が少なくとも１！Ｍ／／ｇ、好ましくは１７ｄｌ／ｇ以
上、更に好ましくは２０〜４０ｄｌ／ｇの範囲の、エチ
レンの単独重合体もしくはエチレンと他のα−オレフィ
ン、例えばプロピレン、１−ブテン、１−ヘキセン、１
−オクテン、４−メチル−１−ペンテン等とのエチレン
を主体とした共重合体で、高結晶性のものである。極限
粘度〔η〕ｅが１５ａｊ／ｇ未満のものは、成形品の機
械的強度が低下する虞れがある。[Function] The ultra-high molecular weight ethylene polymer (A) in the present invention has an intrinsic viscosity [η]e measured in a decalin solvent at 135°C.
is at least 1! homopolymer of ethylene or ethylene and other α-olefins, such as propylene, 1-butene, 1-hexene, 1
- It is a copolymer mainly composed of ethylene with octene, 4-methyl-1-pentene, etc., and is highly crystalline. If the intrinsic viscosity [η]e is less than 15 aj/g, the mechanical strength of the molded product may decrease.
本発明においていう高分子量プロピレン重合体（Ｂ）は
１３５℃デカリン溶媒中で測定した極限粘度〔η〕ｐが
５．Ｏａ／ｇ、好ましくは５．５ｄｌ／ｇ以上、更に好
ましくは５．５〜１５ｄｌ／ｇの範囲の、プロピレンの
単独重合体もしくはプロピレンと他のα−オレフィン、
例えばエチレン、■−ブテン、１−ヘキセン、１−オク
テン、４−メチル−１−ペンテン等又はポリエン類、例
えば、ジビニルベンゼン、１．７−オクタジエン、５−
ビニール−２−ノルボルネン等とのプロピレンを主体と
した共重合体で、高結晶性のものである。極限粘度〔η
〕ｐが５．０７７５未満のものは成形品の機械的強度が
改良されない虞れがある。また高分子量プロピレン重合
体（Ｂ）としては、プロピレンの単独重合体で、高１．
１、例えば９４％以上、更には９６％以上のものが、超
高分子量エチレン重合体組成物の耐熱性、引張強度、剛
性等の向上が図れるので好ましい。The high molecular weight propylene polymer (B) referred to in the present invention has an intrinsic viscosity [η] p of 5. Oa/g, preferably 5.5 dl/g or more, more preferably in the range of 5.5 to 15 dl/g, a homopolymer of propylene or propylene and other α-olefins,
For example, ethylene, -butene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc. or polyenes, such as divinylbenzene, 1,7-octadiene, 5-
It is a copolymer mainly composed of propylene with vinyl-2-norbornene, etc., and is highly crystalline. Intrinsic viscosity [η
] If p is less than 5.0775, the mechanical strength of the molded product may not be improved. The high molecular weight propylene polymer (B) is a propylene homopolymer with a high molecular weight of 1.
1, for example, 94% or more, more preferably 96% or more, since it is possible to improve the heat resistance, tensile strength, rigidity, etc. of the ultra-high molecular weight ethylene polymer composition.
上記超高分子量エチレン重合体（Ａ）と高分子量プロピ
レン重合体（Ｂ）との量的割合は、超高分子量エチレン
重合体（Ａ）が超高分子量エチレン重合体（Ａ）と高分
子量プロピレン重合体（Ｂ）との総重量に対して、１０
〜８５重量％を占める範囲、換言すれば高分子量プロピ
レン重合体（Ｂ）が総重量に対して９０〜１５重量％を
占める範囲である。好ましい量的割合は、超高分子量エ
チレン重合体（Ａ）が総重量に対して１５〜７５重量％
、更に好ましくは２０〜６５重量％を占める範囲である
。超高分子量エチレン重合体（Ａ）が１０重量％未満で
は成形品の衝撃強度、動摩擦係数が悪くなる。一方、９
５重量％を越えるものは、耐熱性、機械的強度等が改良
された成形品が得られない。The quantitative ratio of the ultra-high molecular weight ethylene polymer (A) and the high molecular weight propylene polymer (B) is such that the ultra-high molecular weight ethylene polymer (A) is the same as the ultra-high molecular weight ethylene polymer (A) and the high molecular weight propylene polymer (B). 10 for the total weight with combined (B)
In other words, the high molecular weight propylene polymer (B) accounts for 90 to 15% by weight based on the total weight. A preferable quantitative ratio is that the ultra-high molecular weight ethylene polymer (A) is 15 to 75% by weight based on the total weight.
More preferably, it accounts for 20 to 65% by weight. If the ultra-high molecular weight ethylene polymer (A) is less than 10% by weight, the impact strength and dynamic friction coefficient of the molded article will deteriorate. On the other hand, 9
If the amount exceeds 5% by weight, a molded article with improved heat resistance, mechanical strength, etc. cannot be obtained.
本発明の超高分子量エチレン重合体組成物は、上記の如
き量的割合で超高分子量エチレン重合体（Ａ）と高分子
量プロピレン重合体（Ｂ）とから実質的になる。そして
、本発明の超高分子量エチレン重合体組成物は、１３５
℃デカリン溶媒中で測定した極限粘度〔η〕ｃが６．Ｏ
ａ／ｇ〜４０ｄｌ／ｇの範囲にあり、好ましくは溶融ト
ルクＴが２５ｋｇ−ＣＩ１１以下にあり、且つ極限粘度
〔η〕ｃと溶融トルクＴとの間にＴ≦〔η〕ｃの関係を
有するものである。The ultra-high molecular weight ethylene polymer composition of the present invention consists essentially of an ultra-high molecular weight ethylene polymer (A) and a high molecular weight propylene polymer (B) in the quantitative proportions as described above. And, the ultra-high molecular weight ethylene polymer composition of the present invention has 135
The intrinsic viscosity [η] c measured in decalin solvent is 6. O
a/g to 40 dl/g, preferably the melting torque T is 25 kg-CI11 or less, and the relationship between the intrinsic viscosity [η]c and the melting torque T is T≦[η]c. It is something.
尚、ここで溶融トルクＴは、ＪＳＲキュラストメーター
（今中機械工業■製）を用いて、温度２４０℃、圧力５
ｋｇ／ｃｎ！、振幅±３度、振動数５ ｃ、ｐ、ｍの条
件で測定した値である。極限粘度〔η〕ｃが６．０ｄｌ
／ｇ未満のものは、成形物の機械的強度が低い虞れがあ
る。一方、極限粘度〔η〕ｃが４０ｄｌ／ｇを越えるも
のは成形加工性が損なわれるおそれがある。Here, the melting torque T is determined using a JSR Curastmeter (manufactured by Imanaka Kikai Kogyo) at a temperature of 240°C and a pressure of 5.
kg/cm! , amplitude ±3 degrees, and frequency 5 c, p, m. Intrinsic viscosity [η]c is 6.0 dl
If it is less than /g, the mechanical strength of the molded product may be low. On the other hand, if the intrinsic viscosity [η]c exceeds 40 dl/g, moldability may be impaired.
本発明の垣間分子量エチレン重合体組成物は、好ましく
は極限粘度〔η〕ｃが８〜３０ｄｌ／ｇの範囲にあり、
溶融トルクＴが２Ｑｋｇ−Ｃｍ以下及び〔η〕ｃとＴと
の間にはＴ≦〔η〕 Ｃの関係を有するものである。The marginal molecular weight ethylene polymer composition of the present invention preferably has an intrinsic viscosity [η]c in the range of 8 to 30 dl/g,
The melting torque T is 2Qkg-Cm or less, and the relationship between [η]c and T is T≦[η]C.
本発明の超高分子量エチレン重合体組成物は超高分子量
エチレン重合体（Ａ）と高分子量プロピレン重合体（Ｂ
）とを上記量割合で配合して調製することもできるが、
本発明の他の発明は性能に優れる組成物を得る方法とし
て、高立体規則性重合触媒の存在下にエチレンもしくは
プロピレンのオレフィンを多段階重合法による製法を提
供するものである。The ultra-high molecular weight ethylene polymer composition of the present invention comprises an ultra-high molecular weight ethylene polymer (A) and a high molecular weight propylene polymer (B).
) can also be prepared by blending them in the above amount ratio,
Another aspect of the present invention provides a method for producing a composition with excellent performance by multi-step polymerization of ethylene or propylene olefin in the presence of a highly stereoregular polymerization catalyst.
本発明で利用できる触媒は、プロピレンの高立体規則性
重合を行うことが可能なものであって、既に多くのもの
が知られている。代表的には、チタン触媒成分と有機ア
ルミニウム化合物触媒成分、及び必要に応じ、立体規則
性改善の目的で使用される電子供与体触媒成分とからな
る高立体規則性重合触媒、あるいは、
（Ａ）インデニル基、置換インデニル基およびその部分
水素化物からなる群から選ばれた少なくとも２個の基が
低級アルキレン基を介して結合した多座配位性化合物を
配位子とする周期律表第１ＶＢ族の遷移金属化合物を無
機担体上に担持した固体触媒成分、および
ＣＢ）アルミノオキサン
から形成される高立体規則性重合触媒を例示することが
できる。Many catalysts that can be used in the present invention are already known, and are capable of polymerizing propylene with high stereoregularity. Typically, a highly stereoregular polymerization catalyst consisting of a titanium catalyst component, an organoaluminum compound catalyst component, and, if necessary, an electron donor catalyst component used for the purpose of improving stereoregularity, or (A) Group 1 VB of the periodic table, in which the ligand is a polydentate compound in which at least two groups selected from the group consisting of an indenyl group, a substituted indenyl group, and a partially hydrogenated product thereof are bonded via a lower alkylene group. A highly stereoregular polymerization catalyst formed from a solid catalyst component having a transition metal compound supported on an inorganic carrier and CB) aluminoxane can be exemplified.
チタン触媒成分としては、三塩化チタン触媒成分又はマ
グネシウム化合物、チタン化合物及び電子供与体の相互
反応物を必須成分として含有するマグネシウム化合物担
持型ハロゲン含有チタン触媒成分が代表的なものであり
、いずれも本発明において使用することができるが、活
性が顕著に高いところから後者のタイプのものの使用が
好ましい。Typical titanium catalyst components are titanium trichloride catalyst components or magnesium compound-supported halogen-containing titanium catalyst components containing as essential components an interaction product of a magnesium compound, a titanium compound, and an electron donor. Although they can be used in the present invention, the latter type is preferred because of its significantly higher activity.
三塩化チタン触媒成分としては、四塩化チタンをアルミ
ニウム、チタン、水素、有機アルミニウム化合物などの
還元剤で還元したもの、あるいはこれらをボールミル粉
砕などの機械的粉砕処理及び／又は溶媒洗浄処理〔不活
性溶媒及び／又は極性化合物、例えばエーテル等による
洗浄処理〕。The titanium trichloride catalyst component is titanium tetrachloride reduced with a reducing agent such as aluminum, titanium, hydrogen, or an organoaluminum compound, or mechanically pulverized such as ball milling and/or solvent washed [inert Washing treatment with a solvent and/or a polar compound, such as ether].
四塩化チタン処理等により活性化したものなどを用いる
ことができる。Those activated by titanium tetrachloride treatment or the like can be used.
またマグネシウム化合物、チタン化合物及び電子供与体
の相互反応物を必須成分として含有するハロゲン含有チ
タン触媒成分は、例えば、マグネシウム化合物（又はマ
グネシウム金属）、チタン化合物及び電子供与体を任意
の順序で反応させる方法あるいはさらに上記原料に加え
ハロゲン化剤及び／又は有機アルミニウム化合物の如き
反応助剤を使用して任意の順序で反応させる方法、ある
いは上記各方法で得られるものをさらに溶媒洗浄する方
法などによって得ることができる。このタイプの触媒成
分は、不活性稀釈剤が存在しない□場合は、その比表面
積は通常３ｒｒｒ／ｇ以上、例えば３０ないし１０００
ｒｄ／ｇであり、ハロゲン／Ｔｉ（原子比）が例えば４
ないし１００、好ましくは６ないし７０、Ｍｇ／Ｔｉ
（原子比）が例えば２ないし１００、好ましくは４ない
し７０、電子供与体／Ｔｉ（モル比）がたとえば０．２
ないし１０、好ましくは０．４ないし６の範囲にあり、
通常市販のハロゲン化マグネシウムに比し、非常に非晶
化された状態となっているのが普通である。上記電子供
与体の代表的な例はエステル、エーテル、酸無水物、ア
ルコキシケイ素化合物などである。Further, a halogen-containing titanium catalyst component containing as an essential component an interaction product of a magnesium compound, a titanium compound, and an electron donor can be used, for example, by reacting a magnesium compound (or magnesium metal), a titanium compound, and an electron donor in any order. Alternatively, in addition to the above raw materials, a reaction aid such as a halogenating agent and/or an organoaluminum compound is used to react in any order, or the products obtained by each of the above methods are further washed with a solvent. be able to. This type of catalyst component, in the absence of an inert diluent, usually has a specific surface area of 3 rrr/g or more, e.g.
rd/g, and the halogen/Ti (atomic ratio) is, for example, 4
from 100 to 100, preferably from 6 to 70, Mg/Ti
(atomic ratio) is, for example, 2 to 100, preferably 4 to 70, and electron donor/Ti (molar ratio) is, for example, 0.2.
in the range from 0.4 to 10, preferably from 0.4 to 6;
It is usually in a highly amorphous state compared to commercially available magnesium halides. Typical examples of the electron donor are esters, ethers, acid anhydrides, alkoxy silicon compounds, and the like.
以上の如きチタン触媒成分の製造方法についてはすでに
数多（の方法が知られており、本発明で利用できる。Many methods for producing the titanium catalyst component as described above are already known and can be used in the present invention.
チタン触媒成分としてはまた粒度分布が狭く、かつ球状
、楕円球状あるいはこれらの類似の形状のものが好まし
い。The titanium catalyst component preferably has a narrow particle size distribution and is spherical, ellipsoidal, or similar in shape.
一方、有機アルミニウム化合物触媒成分としては、少な
くとも分子内に１個のＡ１−炭素結合を有する化合物が
利用でき、例えば、（ｉ）一般式Ｒ’、ＡＩ（ＯＲ”）
、ＩＨ，Ｘｑ（ここでＲ１およびＲ２は炭素原子通常工
ないし１５個、好ましくは工ないし４個を含む炭化水素
基、例えば、アルキル基、アリール基、アルケニル基、
シクロアルキル基などで、これらＲ１及びＲ２は、互い
に同一でも異なってもよい。Ｘはハロゲン、ｍは０＜ｍ
≦３、ｎは０≦ｎ＜３、ｐはＯ≦ｐ＜ａ、ｑは０≦ｑ＜
３の数であって、し力１もｍ＋ｎ＋ρ＋＋１＝３である
）で表わされる有機アルミニウム化合物、（ｉｉ ）一
般式Ｍ’ＡＩＲ’４（ここで１はＬｉ、、Ｎａ、 Ｋで
あり、Ｒ１は前記と同じ）で表わされる第１族金属とア
ルミニウムとの錯アルキル化物などを挙げることができ
る。On the other hand, as the organoaluminum compound catalyst component, compounds having at least one A1-carbon bond in the molecule can be used, such as (i) general formula R', AI(OR")
, IH,
These R1 and R2 may be the same or different from each other, such as a cycloalkyl group. X is halogen, m is 0<m
≦3, n is 0≦n<3, p is O≦p<a, q is 0≦q<
(ii) an organoaluminum compound represented by the general formula M'AIR'4 (where 1 is Li, Na, K, and R1 is Examples include complex alkylated products of Group 1 metals and aluminum represented by (same as above).
高立体規則性触媒の形成には、前記したチタン触媒成分
と有機アルミニウム化合物触媒成分の他に、電子供与体
触媒成分を用いてもよい。かかる電子供与体触媒成分と
しては、有機酸エステル、無機酸エステル、アルコキシ
ケイ素化合物、カルボン酸無水物、立体障害アミン類、
これらと塩化アルミニウムの錯体などを例示することが
できる。In addition to the titanium catalyst component and the organoaluminum compound catalyst component described above, an electron donor catalyst component may be used to form the highly stereoregular catalyst. Such electron donor catalyst components include organic acid esters, inorganic acid esters, alkoxy silicon compounds, carboxylic acid anhydrides, sterically hindered amines,
Examples include complexes of these and aluminum chloride.
マグネシウム化合物担持型チタン触媒成分を用いた高活
性高立体規則性触媒の一例としては、例えば特開昭５２
−１５１６９１号、特開昭５３−２１０９３号、特開昭
５５−１３５１０２〜３号、特開昭５６−８１１号、特
開昭５７−６３３１０〜２号、特開昭５８−８３００６
号、特開昭５８−１３８７０５〜１２号などに記載の高
活性高立体規則性触媒系を挙げることができ、本発明で
利用できる。As an example of a highly active and highly stereoregular catalyst using a magnesium compound-supported titanium catalyst component, for example, JP-A-52
-151691, JP 53-21093, JP 55-135102-3, JP 56-811, JP 57-63310-2, JP 58-83006
The highly active and highly stereoregular catalyst systems described in JP-A-58-138705-12 and the like can be mentioned, and can be used in the present invention.
触媒成分（Ａ）における周期律表第１ＶＢ族の遷移金属
として、チタン、ジルコニウム及びハフニウムを挙げる
ことができる。これらの中では、ジルコニウムが好まし
い。Examples of the transition metal of Group 1 VB of the periodic table in the catalyst component (A) include titanium, zirconium, and hafnium. Among these, zirconium is preferred.
触媒成分（Ａ）において上記周律表第ｒＶＢ族の遷移金
属化合物は無機担体上に担持されたものでもよい。担体
としては多孔性無機酸化物が好ましく、具体的には５２
０．、Ａｌｌ ＺＯ：ｌ 、ＭｇＯ１ＺｒＯ，、ＴｌＯ
２、ＢｚＯ，３、ＣａＯ１ＺｎＯ１ＢａＯ１Ｔｈｅ□等
またはこれらの混合物例えば、ＳｉＯ□−ＭｇＯ１Ｓｉ
Ｏ□−Ａ／、０．、ｓｉｏ！−ＴｉＯｔ 、５ｔＯｚ−
ＶｚＯｓ、５ｉＯｚ−ＣｒｚＯ，、Ｓｔｏｗ−ＴｉＯｔ
−ＭｇＯ等を例示することができる。In the catalyst component (A), the transition metal compound of group rVB of the periodic table may be supported on an inorganic carrier. The carrier is preferably a porous inorganic oxide, specifically 52
0. , All ZO:l , MgO1ZrO,, TlO
2, BzO, 3, CaO1ZnO1BaO1The□, etc. or mixtures thereof, e.g., SiO□-MgO1Si
O□-A/, 0. , sio! -TiOt, 5tOz-
VzOs, 5iOz-CrzO,, Stow-TiOt
-MgO etc. can be exemplified.
触媒構成成分のアルミノオキサン（Ｂ）として具体的に
は、一般式ＣＩ）又は一般式ＣＩりＲ２Ａβ−←ＯＡ
１−）−−ＯＡ ｉ Ｒ１ＣＩ ）で表わされる有機ア
ルミニウム化合物を例示することができる。該アルミノ
オキサンにおいて、Ｒはメチル基、エチル基、プロピル
基、ブチル基などの炭化水素基であり、好ましくはメチ
ル基、エチル基とくに好ましくはメチル基であり、ｍは
２以上の整数、好ましくは５以上の整数である。Specifically, as the aluminoxane (B) as a catalyst component, general formula CI) or general formula CI R2Aβ-←OA
1-) -- OA i R1CI ) can be exemplified. In the aluminoxane, R is a hydrocarbon group such as a methyl group, ethyl group, propyl group, butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably is an integer greater than or equal to 5.
該オレフィンの多段重合工程には少なくとも２個以上の
重合槽が通常は直列に連結された多段階重合装置が採用
され、たとえば２段重合法、３段重合法、・・・ｎ段重
合法が実施される。また、１個の重合槽で回分式重合法
により多段階重合法を実施することも可能である。該多
段階重合工程のうち第一段重合工程において超高分子量
エチレレン重合体（Ａ）を生成させることにより耐熱性
、引張強度等が改良された成形品を得ることができる。In the multi-stage polymerization process of the olefin, a multi-stage polymerization apparatus in which at least two or more polymerization vessels are usually connected in series is employed, such as a two-stage polymerization method, a three-stage polymerization method, an n-stage polymerization method, etc. Implemented. It is also possible to perform a multi-stage polymerization method using a batch polymerization method in one polymerization tank. By producing the ultra-high molecular weight ethylene polymer (A) in the first stage polymerization step of the multi-stage polymerization process, a molded article with improved heat resistance, tensile strength, etc. can be obtained.
該重合工程においては、全工程で重合される重合体の１
０〜８５重量％を重合させ、極限粘度〔η）ｅ （デ
カリン溶媒中で１３５℃で測定した値）が少なくとも１
５ｄｌ／ｇの超高分子量エチレン重合体（Ａ）を生成さ
せることが必要であり、さらには全重合工程で重合され
る重合体の１０〜８５重量％、とくに２０〜６５重量％
を重合させることにより、極限粘度（７７） ｅが１７
ｄｌ／ｇ以上、とくに２０〜４０ｄｌ／ｇの超高分子量
エチレン重合体（Ａ）を生成させることが好ましい。重
合工程において、生成する一超高分子量エチレン重合体
（Ａ）の極限粘度〔η〕ｅが１５ｄｌ／ｇ未満であって
も、また該重合工程で生成する超高分子量エチレン重合
体（Ａ）が１０〜８５重量％の範囲を外れても前述の本
発明の超高分子量エチレン重合体組成物の効果が達成で
きない。In the polymerization process, one of the polymers polymerized in the entire process is
0 to 85% by weight, and the intrinsic viscosity [η)e (measured in decalin solvent at 135°C) is at least 1
It is necessary to produce an ultra-high molecular weight ethylene polymer (A) of 5 dl/g, and furthermore, 10 to 85% by weight, especially 20 to 65% by weight of the polymer polymerized in the entire polymerization process.
By polymerizing, the intrinsic viscosity (77) e becomes 17
It is preferable to produce an ultra-high molecular weight ethylene polymer (A) of dl/g or more, particularly 20 to 40 dl/g. In the polymerization step, even if the intrinsic viscosity [η]e of the ultra-high molecular weight ethylene polymer (A) produced is less than 15 dl/g, the ultra-high molecular weight ethylene polymer (A) produced in the polymerization step If the amount is outside the range of 10 to 85% by weight, the above-mentioned effects of the ultra-high molecular weight ethylene polymer composition of the present invention cannot be achieved.
該多段階重合工程において、超高分子量エチレン重合体
（Ａ）を生成させる重合工程では前記高立体規則性重合
触媒の存在下に重合が実施される。In the multi-stage polymerization process, polymerization is carried out in the presence of the highly stereoregular polymerization catalyst in the polymerization process for producing the ultra-high molecular weight ethylene polymer (A).
また必要に応じて、本重合工程に先立って予備重合を行
っても良い。予備重合は、不活性炭化水素溶媒中で、又
は液状単量体を溶媒として、又は溶媒を用いないで炭素
数２ないしｌＯのα−オレフィンを予備重合させる。か
かる処理により、得られる共重合体のポリマー粒子性状
が改良される。重合は気相重合法で実施することもでき
るし、液相重合法で実施することもできる。いずれの場
合にも、超高分子量エチレン重合体（Ａ）を生成させる
重合工程では、重合反応は必要に応じて不活性媒体の存
在下に実施される。たとえば気相重合法では必要に応じ
て不活性媒体からなる稀釈剤の存在下に実施され、液相
重合法では必要に応じて不活性媒体からなる溶媒下に実
施される。Further, if necessary, preliminary polymerization may be performed prior to the main polymerization step. In the prepolymerization, an α-olefin having 2 to 1 O carbon atoms is prepolymerized in an inert hydrocarbon solvent, using a liquid monomer as a solvent, or without using a solvent. Such treatment improves the polymer particle properties of the resulting copolymer. Polymerization can be carried out by gas phase polymerization or liquid phase polymerization. In either case, in the polymerization step for producing the ultra-high molecular weight ethylene polymer (A), the polymerization reaction is carried out in the presence of an inert medium, if necessary. For example, gas phase polymerization is carried out in the presence of a diluent consisting of an inert medium, if necessary, and liquid phase polymerization is carried out, if necessary, in the presence of a diluent consisting of an inert medium.
前記超高分子量エチレン重合体（Ａ）を生成させる重合
工程の温度は通常約−２０〜約１２０℃、好ましくは約
０〜約１００℃、とくに好ましくは約５−約９５℃の範
囲である。また、重合反応の際の圧力は、前記温度で液
相重合又は気相重合が可能な圧力範囲であり、例えば大
気圧〜約１００ｋｇ／ｃｆｆｌ、好ましくは大気圧〜約
５０ ｋｇ ／ ｃｔ＆の範囲である。また、重合工程
における重合時間は、特に制限はないが、通常１〜１５
００分、好ましくは５〜１０００分である。The temperature of the polymerization step for producing the ultra-high molecular weight ethylene polymer (A) is usually in the range of about -20 to about 120°C, preferably about 0 to about 100°C, particularly preferably about 5 to about 95°C. Further, the pressure during the polymerization reaction is within a pressure range that allows liquid phase polymerization or gas phase polymerization at the above temperature, for example, atmospheric pressure to about 100 kg/cffl, preferably atmospheric pressure to about 50 kg/ct&. be. In addition, the polymerization time in the polymerization step is not particularly limited, but is usually 1 to 15
00 minutes, preferably 5 to 1000 minutes.
また、該重合工程において、前記超高分子量エチレン重
合体（Ａ）を生成させるためには、該重合反応を水素の
不存在下に実施するのが好ましい。さらには、該重合反
応を実施後、重合体を不活性媒体雰囲気下で一旦単離し
、保存しておくことも可能である。Moreover, in the polymerization step, in order to produce the ultra-high molecular weight ethylene polymer (A), it is preferable to carry out the polymerization reaction in the absence of hydrogen. Furthermore, after carrying out the polymerization reaction, it is also possible to temporarily isolate and store the polymer under an inert medium atmosphere.
該超高分子量エチレン重合体（Ａ）を生成させる重合工
程において使用することのできる不活性媒体としては、
例えばプロパン、ブタン、ペンタン、ヘキサン、ヘプタ
ン、オクタン、デカン、灯油などの脂肪族炭化水素；シ
クロペンタン、シクロヘキサンなどの脂環族炭化水素；
ベンゼン、トルエン、キシレンなどの芳香族炭化水素；
ジクロルエタン、メチレンクロリド、クロルベンゼンな
どのハロゲン化炭化水素；あるいはこれらの混合物など
を挙げることができる。とくに脂肪族炭化水素の使用が
望ましい。Inert media that can be used in the polymerization step to produce the ultra-high molecular weight ethylene polymer (A) include:
For example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, kerosene; alicyclic hydrocarbons such as cyclopentane and cyclohexane;
Aromatic hydrocarbons such as benzene, toluene, and xylene;
Examples include halogenated hydrocarbons such as dichloroethane, methylene chloride, and chlorobenzene; or mixtures thereof. Particularly desirable is the use of aliphatic hydrocarbons.
また、本発明において、前記超高分子量エチレン重合体
（Ａ）を生成させる重合工程につづくプロピレンの重合
工程においては実質的に水素の不存在下にプロピレンも
しくはプロピレンを主体としたモノマーの重合反応が実
施される。第二の重合工程には該超高分子量エチレン重
合体（Ａ）が供給され、連続して重合が実施される。そ
の際、当該重合工程にはプロピレンが供給される。また
その際、他のα−オレフィンやポリエン類を同時に供給
しても良い。好適なα−オレフィンとしては炭素数２な
いし１０のα−オレフィンであり、またポリエン顛とし
ては、ジビニルベンゼン、１，７−オクタジエン、５−
ビニル−２−ノルボルネンが例示できる。当該重合工程
では、前段階で生成した重合生成液中に含まれている触
媒をそのまま使用することもできるし、必要に応じて前
記高立体規則性重合触媒を追加補充しても差しつかえな
い。当該重合工程で重合される高分子量プロピレン重合
体（Ｂ）の割合は、全重合工程で重合される全重合体に
対して９０〜１５重世％、好ましくは８５〜２５重千％
、とくに好ましくは８０〜３５重量％の範囲である。Furthermore, in the present invention, in the propylene polymerization step following the polymerization step for producing the ultra-high molecular weight ethylene polymer (A), the polymerization reaction of propylene or a monomer mainly composed of propylene is carried out in the substantial absence of hydrogen. Implemented. The ultra-high molecular weight ethylene polymer (A) is supplied to the second polymerization step, and polymerization is continuously carried out. In this case, propylene is supplied to the polymerization step. Further, at that time, other α-olefins and polyenes may be supplied at the same time. Suitable α-olefins include α-olefins having 2 to 10 carbon atoms, and examples of polyenes include divinylbenzene, 1,7-octadiene, 5-
An example is vinyl-2-norbornene. In the polymerization step, the catalyst contained in the polymerization solution produced in the previous step can be used as is, or the highly stereoregular polymerization catalyst can be additionally replenished as necessary. The proportion of the high molecular weight propylene polymer (B) polymerized in the polymerization step is 90 to 15% by weight, preferably 85 to 25% by weight based on the total polymer polymerized in the entire polymerization step.
, particularly preferably in the range of 80 to 35% by weight.
高分子量プロピレン重合体（Ｂ）の重合工程の重合温度
は液相重合、気相重合が可能な温度範囲で、約０〜約１
００℃、更には約５〜約９５℃の範囲が好ましい。また
重合圧力は、例えば大気圧〜約１００ｋｇ ／ ｃｎｌ
、と（には大気圧〜約５０ｋｇ／ｃｎｌの範囲が推奨
できる。そして重合時間は特に制限はないが、通常１〜
１５００分、好ましくは５〜１０００分である。The polymerization temperature in the polymerization step of the high molecular weight propylene polymer (B) is within a temperature range that allows liquid phase polymerization and gas phase polymerization, and is about 0 to about 1
00°C, more preferably in the range of about 5 to about 95°C. Moreover, the polymerization pressure is, for example, atmospheric pressure to about 100 kg/cnl.
For , and (, a range of atmospheric pressure to about 50 kg/cnl is recommended. There is no particular restriction on the polymerization time, but it is usually 1 to 50 kg/cnl.
1500 minutes, preferably 5 to 1000 minutes.
高分子量プロピレン重合体（Ｂ）の重合工程は同様に気
相重合法で実施することもできるし、液相重合法で実施
することもできる。もちろん各重合工程で異なる重合方
法を採用することも可能である。液相重合法のうちでは
スラリー懸濁重合法が好適に採用される。いずれの場合
にも、該重合工程では重合反応は通常は不活性媒体の存
在下に実施される。たとえば気相重合法では不活性媒体
稀釈剤の存在下に実施され、液相スラリー懸濁重合法で
は不活性媒体溶媒の存在下に実施される。不活性媒体と
しては前記超高分子量エチレン重合体（Ａ）を生成させ
る重合工程において例示した不活性媒体と同じものを例
示することができる。The polymerization step of the high molecular weight propylene polymer (B) can be similarly carried out by a gas phase polymerization method, or can also be carried out by a liquid phase polymerization method. Of course, it is also possible to employ different polymerization methods in each polymerization step. Among the liquid phase polymerization methods, a slurry suspension polymerization method is preferably employed. In either case, the polymerization reaction is usually carried out in the presence of an inert medium in the polymerization step. For example, gas phase polymerization processes are carried out in the presence of an inert medium diluent, and liquid phase slurry suspension polymerization processes are carried out in the presence of an inert medium solvent. Examples of the inert medium include the same inert media exemplified in the polymerization step for producing the ultra-high molecular weight ethylene polymer (A).
最終段階の重合工程で得られる超高分子量エチレン重合
体組成物〔η〕ｃが通常は６〜４０ｄｌ／ｇ、好ましく
は８〜３０ｄｌ ／ ｇ 、溶融トルクが２５ｋｇ−Ｃ
ｍ以下、好ましくは２９ｋｇ−ｃｍとなるように重合反
応が実施される。The ultra-high molecular weight ethylene polymer composition [η]c obtained in the final polymerization step is usually 6 to 40 dl/g, preferably 8 to 30 dl/g, and the melting torque is 25 kg-C.
The polymerization reaction is carried out so that the weight is less than m, preferably 29 kg-cm.
前記多段階重合法は、回分式、半連続式又は連続式のい
ずれかの方法でも実施することができる。The multi-step polymerization method can be carried out in a batch, semi-continuous or continuous manner.
本発明の超高分子量エチレン重合体組成物を多段階重合
法で製造する際には、先に超高分子量エチレン重合体（
Ａ）を生成し、次いで高分子量プロピレン重合体（Ｂ）
を生成させて製造する必要がある。先に高分子量プロピ
レン重合体（Ｂ）を生成する方法で得られる組成物は、
耐熱性が改良されず、引張強度も低下する。When producing the ultra-high molecular weight ethylene polymer composition of the present invention by a multi-step polymerization method, the ultra-high molecular weight ethylene polymer (
A) and then a high molecular weight propylene polymer (B)
It is necessary to generate and manufacture. The composition obtained by the method of first producing a high molecular weight propylene polymer (B) is
Heat resistance is not improved and tensile strength is also reduced.
本発明の超高分子量エチレン重合体組成物は、公知の熱
可塑性樹脂の成形法である、押出成形、圧縮成形、射出
成形、回転成形をはじめ、これらの応用成形技術等によ
り種々の成形品に成形することができる。The ultra-high molecular weight ethylene polymer composition of the present invention can be made into various molded products by known thermoplastic resin molding methods such as extrusion molding, compression molding, injection molding, rotational molding, and other applied molding techniques. Can be molded.
本発明の超高分子量エチレン重合体組成物には、耐熱安
定剤、耐候安定剤、帯電防止剤、防曇剤、抗ブロツキン
グ剤、スリップ剤、滑剤、核剤、Ｄｎ料、染料、カーボ
ンブラック、タルク、ガラス粉、ガラス繊維等の無機充
填剤あるいは補強剤、有機充填剤あるいは補強剤、難燃
剤、中性子遮蔽剤等、通常ポリオレフィンに添加使用さ
れる種々公知の添加剤を本発明の目的を損わない範囲で
配合しておいてもよい。The ultra-high molecular weight ethylene polymer composition of the present invention includes a heat stabilizer, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, a nucleating agent, a Dn additive, a dye, carbon black, Inorganic fillers or reinforcing agents such as talc, glass powder, glass fibers, organic fillers or reinforcing agents, flame retardants, neutron shielding agents, and various other known additives that are normally added to polyolefins may be used to defeat the purpose of the present invention. It may be blended within a range that does not cause
本発明の超高分子量エチレン重合体組成物は、従来の超
高分子量ポリエチレンあるいは超高分子量ポリエチレン
に改質剤として低分子量ポリエチレンもしくはポリプロ
ピレン等を添加した組成物に比べて更に成形加工性が優
れ、しかも本組成物から得られる成形品の引張強度、剛
性、耐熱性も優れ、且つ超高分子量ポリエチレンが本来
有する優れた性質である耐衝撃性、自己潤滑性、耐摩耗
性、耐薬品性も損われないという特徴を有している。そ
れ故、かかる特性を活かして、ＯＡ機器、家電、自動車
、一般機械、建築資材等の機能部品材料として有効に用
いることができる。The ultra-high molecular weight ethylene polymer composition of the present invention has superior moldability compared to conventional ultra-high molecular weight polyethylene or compositions prepared by adding low molecular weight polyethylene or polypropylene as a modifier to ultra-high molecular weight polyethylene. In addition, the molded products obtained from this composition have excellent tensile strength, rigidity, and heat resistance, and also have excellent properties inherent to ultra-high molecular weight polyethylene, such as impact resistance, self-lubricating property, abrasion resistance, and chemical resistance. It has the characteristic of not being damaged. Therefore, by taking advantage of such properties, it can be effectively used as a material for functional parts of OA equipment, home appliances, automobiles, general machinery, construction materials, etc.
実施例１
（Ｉ）固体Ｔｉ触媒成分（ａ）の調製
無水塩化マグネシウム４．７６ ｇ （５０ｍｍｏｌ）
、デカン２５−および２−エチルヘキシルアルコール２
３．４ｍＺ（１５０ｍｍｏｌ）を１３０℃で２時間加熱
反応を行い均一溶液とした後、この溶液中に無水フタル
酸１．１１ｇ（７，５ｍｍｏｌ）を添加し、１３０℃に
て更に１時間撹拌部合を行い、無水フタル酸を該均一溶
液に溶解させる。この様にして得られた均一溶液を室温
に冷却した後、−２０℃にて保持された四塩化チタン２
００ｍＺ（１，８ｍｏｌ）中に１時間に互って全量滴下
装入する。Example 1 (I) Preparation of solid Ti catalyst component (a) Anhydrous magnesium chloride 4.76 g (50 mmol)
, decane 25- and 2-ethylhexyl alcohol 2
After heating and reacting 3.4mZ (150 mmol) at 130°C for 2 hours to make a homogeneous solution, 1.11g (7.5 mmol) of phthalic anhydride was added to this solution, and the mixture was stirred at 130°C for an additional 1 hour. The phthalic anhydride is dissolved in the homogeneous solution. After cooling the homogeneous solution obtained in this way to room temperature, titanium tetrachloride 2 was kept at -20°C.
The entire amount was added dropwise to 00mZ (1.8 mol) over 1 hour.
装入終了後、この混合液の温度を４時間かけて１００℃
に昇温し、１１０℃に達したところでジイソブチルフタ
レート２．６８ｍｆ （１２，５ｍｍｏｌ）を添加し、
これより２時間同温度にて攪拌上保持する。２時間の反
応終了後熱濾過にて固体部を採取し、この固体部を２０
０ ＋ｎＺのＴｉＣｊ２ｎにて再懸濁させた後、再び１
１０℃で２時間、加熱反応を行う。反応終了後、再び熱
濾過にて固体部を採取し、１１０℃デカン及びヘキサン
にて、洗液中に遊離のチタン化合物が検出されなくなる
迄精製へキサンで充分で洗浄する。After charging, the temperature of this mixture was increased to 100°C over 4 hours.
When the temperature reached 110°C, 2.68 mf (12.5 mmol) of diisobutyl phthalate was added.
From this point on, the mixture was stirred and maintained at the same temperature for 2 hours. After 2 hours of reaction, the solid part was collected by hot filtration, and this solid part was
After resuspending in TiCj2n of 0 +nZ, resuspending with 1
The heating reaction is carried out at 10° C. for 2 hours. After completion of the reaction, the solid portion is again collected by hot filtration and washed with sufficient purified hexane at 110°C with decane and hexane until no free titanium compound is detected in the washing liquid.
以上の製造方法にて合成された固体Ｔｉ触媒成分はヘキ
サンスラリーとして保存するが、このうち一部を触媒組
成を調べる目的で乾燥する。この様にして得られた固体
Ｔｉ触媒成分の組成はチタン３．１重量％、塩素５６．
０重量％、マグネシウム１７．０重量％およびジイソブ
チルフタレート２０．９重量％であった。The solid Ti catalyst component synthesized by the above production method is stored as a hexane slurry, and a portion of this is dried for the purpose of examining the catalyst composition. The composition of the solid Ti catalyst component thus obtained was 3.1% by weight of titanium and 56% by weight of chlorine.
0% by weight, 17.0% by weight of magnesium and 20.9% by weight of diisobutyl phthalate.
（ＩＩ）予備重合
窒素雰囲気中４００ｒｎ１の攪拌器付口ツ目ガラス製反
応器に、精製へキサン１５０−、トリエチルアルミニウ
ム１５ｍｍｏｌ、ジフェニルジメトキシシラン３ ｍｍ
ｏｌ及び前記チタン触媒成分（ａ）をチタン原子換算で
１．５ｍｍｏｌ添加した後、プロピレンを３．７Ｎ（ｔ
／ｇｒの速度で上記混合物中に１時間フィードした。こ
の間の温度は２０℃に保った。プロピレンフィード開始
後１時間してプロピレンのフィード゛ を止め、代っ
て窒素をフィードし、反応器内を窒素置換した。攪拌を
止め静置汲上澄液を除去し、新たに精製ヘキサン１５０
ｒＩｉを加えた。この洗浄操作を３回くり返した後、再
度ヘキサンにリスラリ−し、保存用触媒ビンに移液した
。予備重合量は３ ｇ −ＰＰ／ ｇ触媒であった。(II) Prepolymerization In a nitrogen atmosphere, 150 mmol of purified hexane, 15 mmol of triethylaluminum, and 3 mm of diphenyldimethoxysilane were placed in a 400rn1 open-mouthed glass reactor equipped with a stirrer.
After adding 1.5 mmol of titanium catalyst component (a) and the titanium catalyst component (a), propylene was added at 3.7N (t
/gr for 1 hour into the above mixture. During this time, the temperature was maintained at 20°C. One hour after the start of propylene feed, the propylene feed was stopped and nitrogen was fed instead to replace the inside of the reactor with nitrogen. Stop stirring, remove the supernatant liquid, and add 150 ml of purified hexane.
rIi was added. After repeating this washing operation three times, the slurry was re-slurried in hexane and transferred to a catalyst bottle for storage. The amount of prepolymerization was 3 g-PP/g catalyst.
（Ｉ［［）本重合
内容積２Ｎのオートクレーブに精製ヘキサン７５０ ｍ
Ｚを装入する。トリエチルアルミニウム０．７５ｍｍｏ
Ｌジフェニルジフェニルジメトキシシラン０ｍｏｌおよ
び前記（ｒｌ）で予備重合処理された触媒成分をチタン
原子に換算して０．０７５ｍｍｏｌ装入して攪拌した。(I
Charge Z. Triethyl aluminum 0.75 mmo
0 mol of L diphenyldiphenyldimethoxysilane and 0.075 mmol of the catalyst component prepolymerized with the above (rl) in terms of titanium atoms were charged and stirred.
その後、５０℃まで昇温してエチレンの供給をはじめ、
５０℃で全圧８．０ｋｇ ／ ｃｔＡ Ｇを維持するよ
う５時間に亙って供給して重合を行った（第１段階）。After that, the temperature was raised to 50℃ and the supply of ethylene was started.
Polymerization was carried out at 50° C. by supplying over 5 hours to maintain a total pressure of 8.0 kg/ctAG (first stage).
この時の重合体の極限粘度〔η〕は３２．７ｄｌ／ｇで
あった。その後、すばやく系内のエチレンをパージし、
７０℃まで昇温した。次いで、プロピレンを全圧が７．
０ｋｇ／ｃＪＧになるまで張り込んで再び重合を開始し
た。全圧が７．０ｋｇ／ｃ＋ｄＧを維持する様にプロピ
レンを連続的に導入し、４時間重合を行った（第２段階
）。The intrinsic viscosity [η] of the polymer at this time was 32.7 dl/g. After that, quickly purge the ethylene in the system,
The temperature was raised to 70°C. Next, propylene was added to a total pressure of 7.
The pressure was increased to 0 kg/cJG and polymerization was started again. Propylene was continuously introduced so that the total pressure was maintained at 7.0 kg/c+dG, and polymerization was carried out for 4 hours (second stage).
重合終了後、降温、脱圧し、重合体を得た。After the polymerization was completed, the temperature was lowered and the pressure was removed to obtain a polymer.
得られた重合体の収量は２５６ｇで赤外吸収スペクトル
による定量により、プロピレン含量は６３重量％であり
、全体のポリマーの極限粘度〔η〕。The yield of the obtained polymer was 256 g, and as determined by infrared absorption spectroscopy, the propylene content was 63% by weight, and the intrinsic viscosity of the entire polymer was [η].
は１７．３ｄｌ／ｇ （デカリン中、 １３５℃）、
溶融トルクは１２ｋｇ−ｃｍであった。〔η〕の測定は
以下の方法で行った。is 17.3 dl/g (in decalin, 135°C),
The melting torque was 12 kg-cm. [η] was measured using the following method.
〔η） ： １３５℃デカリン溶媒中で測定した極
限粘度。[η): Intrinsic viscosity measured in decalin solvent at 135°C.
なお、第２段階以降に生成したポリマーの極限粘度は可
成性が成り立つとして、計算により求めた。Note that the intrinsic viscosity of the polymer produced after the second stage was determined by calculation on the assumption that composition was established.
溶融トルクの測定は以下の方法で行った。Melting torque was measured by the following method.
溶融トルク（Ｔ） ： ＪＳＲキュラストメーター
（今用機械工業製）を用い、温度２４０℃、圧力５ ｋ
ｇ ／ ｃＪ、振幅±３度、振動数６ＣＰＭで測定した
溶融状態の試料の応力トルクである。Melting torque (T): Using JSR Curastmeter (manufactured by Imyo Kikai Kogyo), temperature 240°C, pressure 5k
g/cJ, the stress torque of the sample in the molten state measured at an amplitude of ±3 degrees and a frequency of 6 CPM.
（ＩＶ）物性の評価
〈圧縮成形〉
前記ポリオレフィン組成物１００重量部と配合剤として
ステアリン酸カルシウム （日本樹脂側型） ０．１１
ｆｆｉ部とを小型ヘンシェルミキサーで混合後、圧縮成
形機（東邦プレス５０Ｔｓ）を用いて以下の条件下で円
板（１８０ｍｍφｘ ３．２ｔｍｍ）を成形後切削して
試験片を作成した。(IV) Evaluation of physical properties (compression molding) 100 parts by weight of the polyolefin composition and 0.11 parts of calcium stearate (Nippon Resin side type) as a compounding agent
After mixing with the ffi part using a small Henschel mixer, a test piece was prepared by molding and cutting a disk (180 mmφ x 3.2 tmm) using a compression molding machine (Toho Press 50Ts) under the following conditions.
金型： １８０ｍｍφ円板用（ピストン・シリンダー
）加熱条件
温度＝２２０°Ｃ
圧 カニ １００ｋｇ／ｃＪ （最初の５分間）５０
ｋｇ／ＣｒＡ（５分経過後）
時 間ニドータル２０分間
冷却条件
温 度＝２０℃（通水冷却）
圧 カニ５０ｋｇ／ｃｄ（最初の１分間）１００ ｋｇ
／ ｃＩ＋！ （１分経過後）時 間ニドータル１５分
間
試料の物性評価を以下の方法で行った。Mold: For 180mmφ disc (piston/cylinder) Heating conditions Temperature = 220°C Pressure Crab 100kg/cJ (first 5 minutes) 50
kg/CrA (after 5 minutes) Time Nidortal 20 minute cooling conditions Temperature = 20°C (water cooling) Pressure Crab 50 kg/cd (first minute) 100 kg
/cI+! (After 1 minute) The physical properties of the sample were evaluated using the following method for 15 minutes.
引張試験： ＡＳＴＭ Ｄ ６３Ｂ、但し試験片形状を
ＡＳＴＭ４号及び引張速度を５０ｍｍ／ｍｉｎとし、降
伏点応力（ＹＳ ： ｋｇ／ ｃ＋＋ｆ） 、破断点抗
張力（ＴＳ ： ｈｇ／ｃシ）、ヤング率（Ｅ ： ｋ
ｇ／ｃｎｌ）及び破断点伸び（ＥＬ：％）を求めた。Tensile test: ASTM D 63B, however, the test piece shape was ASTM 4 and the tensile speed was 50 mm/min, and the yield point stress (YS: kg/c++f), tensile strength at break (TS: hg/c), Young's modulus (E : k
g/cnl) and elongation at break (EL:%) were determined.
ビカット軟化点（℃）：ヒートデイストーションテスタ
ー（東洋精機型）を用い、
ＡＳＴＭ Ｄ １５２５に準じる。Vicat Softening Point (°C): According to ASTM D 1525 using a heat distortion tester (Toyo Seiki model).
オルゼン剛性（ｋｇ／ｃｏり ： ＡＳＴＭ Ｄ ７
４７に準じる。Olsen stiffness (kg/coli: ASTM D 7)
47.
ダインシュタット衝撃強度（ｋｇ−ＣＩＩＩｌｏＩｌｌ
）：テストピース： ３ Ｘ ５ Ｘ１５ｍｍ試験機：
東洋精機製作所型
ダインシュタラトチスフ−
動摩擦係数：松原式摩擦摩耗試験機（東洋ボールドウィ
ン製）を用いて圧縮荷重５
ｋｇ ／ ｃｆｆｌ及びｌ Ｑ ｋｇ ／ ａｌ！、す
べり速度１２ｍ／ｍｔｎの条件下各３０分間行い摩擦係
数を求めた。相手材はＳＯＳ ３０４、摺動面粗度は６
Ｓに加工して用いた。Duinstadt impact strength (kg-CIIIloIll)
): Test piece: 3 x 5 x 15mm testing machine:
Toyo Seiki Seisakusho type Dainstalat Tisfu - Coefficient of dynamic friction: Compressive load 5 kg/cffl and lQ kg/al! using Matsubara type friction and wear tester (manufactured by Toyo Baldwin). The friction coefficient was determined for 30 minutes each under conditions of a sliding speed of 12 m/mtn. The mating material is SOS 304, and the sliding surface roughness is 6.
It was processed into S and used.
これらの結果を表１に示す。These results are shown in Table 1.
実施例２
実施例１ （■）において、第２段階のプロピレンの重
合時間を３時間とすることを除いては実施例１ （■）
と同様の方法で重合を行った。Example 2 Example 1 (■) except that the polymerization time of propylene in the second stage was 3 hours.
Polymerization was carried out in the same manner as.
得られた重合の収量は２１１ｇであり、プロピレン含量
は５５重量％、極限粘度は１７．０ｄｌ／ｇ、トルクは
１３ｋｇ・ｃｍであった。この重合体を実施例１（ＩＶ
）に従って物性の測定を行った。得られた結果は表１に
示す通りである。The yield of the obtained polymerization was 211 g, the propylene content was 55% by weight, the intrinsic viscosity was 17.0 dl/g, and the torque was 13 kg·cm. This polymer was prepared in Example 1 (IV
) The physical properties were measured according to the method. The results obtained are shown in Table 1.
実施例３．４
実施例１ （■）において、第１段階のエチレンの重合
温度と重合時間および第２段階のプロピレンの重合温度
と重合時間を変えること以外は実施例１と同様にして重
合を行った。得られた結果は表１に示す通りである。Example 3.4 In Example 1 (■), polymerization was carried out in the same manner as in Example 1, except that the polymerization temperature and polymerization time of ethylene in the first stage and the polymerization temperature and polymerization time of propylene in the second stage were changed. went. The results obtained are shown in Table 1.
比較例１
実施例１ （■）において、第１段階のエチレンの重合
温度を６５℃、重合時間を１．０時間とし、更に第２段
階のプロピレンの重合時間を４５分とした以外は実施例
１と同様にして重合を行った。得られた重合体の収量は
１０６ｇで、プロピレン含量は１０重量％であり、極限
粘度は１９．３ｄｌ／ ｇ 、溶融トルクは３１ｋｇ−
ｃｍであった。この重合体の評価を実施例１と同様に行
った。結果を表２に示す。Comparative Example 1 Example 1 (■) except that the ethylene polymerization temperature in the first stage was 65°C and the polymerization time was 1.0 hours, and the propylene polymerization time in the second stage was 45 minutes. Polymerization was carried out in the same manner as in 1. The yield of the obtained polymer was 106 g, the propylene content was 10% by weight, the intrinsic viscosity was 19.3 dl/g, and the melting torque was 31 kg-
It was cm. This polymer was evaluated in the same manner as in Example 1. The results are shown in Table 2.
比較例２
内容積２１のオートクレーブに精製へキサン７５０ ｍ
ｌを装入する。トリエチルアルミニウム０．７５ｍｍｏ
Ｌジフェニルジメトキシシラン０．０７５ｍｍｏｌおよ
び予備重合処理された触媒成分をチタン原子に換算して
０．０７５ｍｍｏｌ装入して攪拌した。その後、７０℃
まで昇温しでプロピレンの供給をはじめ７０℃で全圧７
．０ｋｇ／ｃｄＱを維持するよう２．５時間に互って供
給して重合を行った（第１段階）。その後、５０℃まで
降温させ、系内のプロピレンをパージした後、６５℃ま
で昇温してエチレンを全圧が８．０ｋｇ ／ ｃｉ Ｇ
となるまで張り込んで再び重合を開始した。全圧が８．
０ｋｇ／ａａＧを維持するように、エチレンを連続的に
導入して４．５時間重合を行った（第２段階）。Comparative Example 2 750 m of purified hexane was placed in an autoclave with an internal volume of 21 m
Charge l. Triethyl aluminum 0.75 mmo
0.075 mmol of L diphenyldimethoxysilane and 0.075 mmol of the prepolymerized catalyst component in terms of titanium atoms were charged and stirred. After that, 70℃
The temperature was raised to 70°C and the total pressure was 7.
．． Polymerization was carried out by feeding each other for 2.5 hours to maintain 0 kg/cdQ (first stage). After that, the temperature was lowered to 50°C, and after purging the propylene in the system, the temperature was raised to 65°C, and the ethylene was heated to a total pressure of 8.0 kg/ci G.
The polymerization was started again by increasing the pressure until the temperature reached . The total pressure is 8.
Ethylene was continuously introduced and polymerization was carried out for 4.5 hours so as to maintain 0 kg/aaG (second stage).
重合終了後、降温、脱圧し、重合体を得た。After the polymerization was completed, the temperature was lowered and the pressure was removed to obtain a polymer.
得られた重合体の収量は４３５ｇで、プロピレン含量は
２３重量％であり、極限粘度は１７．１ｄｌ／ｇ、トル
クは２８ｋｇ−ｃｍであった。The yield of the obtained polymer was 435 g, the propylene content was 23% by weight, the intrinsic viscosity was 17.1 dl/g, and the torque was 28 kg-cm.
比較例３
実施例１ （１）の第１段階終了後に、系内のエチレン
をパージした後、７０℃まで昇温した。その後、水素を
１．Ｏｊ２添加し、ひきつづいて、プロピレンを全圧が
１．０ｋｇ／ｃＡＧになるまで張り込んで、再び重合を
開始した。全圧が７．０ｋｇ／ｃＪＧを維持するように
プロピレンを連続的に導入し、３時間重合を行った。Comparative Example 3 After completing the first stage of Example 1 (1), the ethylene in the system was purged, and then the temperature was raised to 70°C. Then add 1. Oj2 was added, and propylene was subsequently charged until the total pressure reached 1.0 kg/cAG to start polymerization again. Propylene was continuously introduced so that the total pressure was maintained at 7.0 kg/cJG, and polymerization was carried out for 3 hours.
重合終了後、降温、脱圧し、重合体を得た。After the polymerization was completed, the temperature was lowered and the pressure was removed to obtain a polymer.
得られた重合体の収量は２７９ｇで、赤外線吸収スペク
トルによる定量によりプロピレン含量は６６重量％であ
り、極限粘度は１２．２ｄｌ／ ｇ、トルクは６．５
ｋｇ−ｃｍであった。The yield of the obtained polymer was 279 g, the propylene content was 66% by weight as determined by infrared absorption spectrum, the intrinsic viscosity was 12.2 dl/g, and the torque was 6.5.
kg-cm.
この重合体を実施例１と同様に評価した。結果を表１に
示す。This polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.
参考例１
内容積２１のオートクレーブに精製ヘキサン７５０ ｒ
ｎｌを装入する。トリエチルアルミニウム０．７５ｍｍ
ｏＬジフェニルジメトキシシラン０．０７５ｍｍｏｌお
よび予備重合処理された触媒成分をチタン原子に換算し
て０．０７５ｍｍｏｌ装入して攪拌した。その後、７０
°Ｃまで昇温しでエチレンの供給をはじめ７０℃で全圧
６．０ｋｇ ／ ｃｔＡ Ｇを維持するよう５時間に亙
って供給して重合を行った。Reference example 1 Purified hexane 750 r in an autoclave with an internal volume of 21
Charge nl. Triethyl aluminum 0.75mm
0.075 mmol of oL diphenyldimethoxysilane and 0.075 mmol of the prepolymerized catalyst component in terms of titanium atoms were charged and stirred. After that, 70
The temperature was raised to .degree. C., and ethylene was then supplied for 5 hours to maintain a total pressure of 6.0 kg/ctAG at 70.degree. C. for polymerization.
重合終了後、降温、脱圧し、ポリプロピレン成分を全く
製造せずに重合体を得た。得られた重合体の収量は１９
８ｇで、極限粘度は１７．４ｄｌ／ｇ（デカリン中、
１３５℃）、トルクは４２ｋｇ−ａｍであった。After the polymerization was completed, the temperature was lowered and the pressure was removed to obtain a polymer without producing any polypropylene component. The yield of the obtained polymer was 19
8g, the intrinsic viscosity is 17.4dl/g (in decalin,
135° C.), and the torque was 42 kg-am.
この重合体を実施例１と同様に評価した。結果を表２に
示す。This polymer was evaluated in the same manner as in Example 1. The results are shown in Table 2.
Claims (2)
粘度〔η〕ｅが少なくとも１５ｄｌ／ｇの超高分子量エ
チレン重合体（Ａ）と１３５℃デカリン溶媒中で測定し
た極限粘度〔η〕ｐが少 なくとも５．０ｄｌ／ｇの高分子量プロピレン重合体（
Ｂ）とから実質的になり、 （II）上記超高分子量エチレン重合体（Ａ）は該超高分
子量エチレン重合体（Ａ）と高分子量プロピレン重合体
（Ｂ）との総重量に対し１０〜８５重量％の範囲にあり
、 （III）１３５℃デカリン溶媒中で測定した極限粘度〔
η〕ｃが６．０ｄｌ／ｇ〜４０ｄｌ／ｇの範囲である、 ことを特徴とする超高分子量エチレン重合体組成物。(1) (I) Ultra-high molecular weight ethylene polymer (A) with an intrinsic viscosity [η]e measured in a decalin solvent at 135°C of at least 15 dl/g and an intrinsic viscosity [η]p measured in a decalin solvent at 135°C of a high molecular weight propylene polymer (
B), and (II) the ultra-high molecular weight ethylene polymer (A) is 10 to 10% based on the total weight of the ultra-high molecular weight ethylene polymer (A) and the high molecular weight propylene polymer (B). (III) Intrinsic viscosity measured in decalin solvent at 135°C [
η]c is in the range of 6.0 dl/g to 40 dl/g, an ultra-high molecular weight ethylene polymer composition.
程において極限粘度が少なくとも１５ｄｌ／ｇの超高分
子量エチレン重合体（Ａ）を１０〜８５重量％生成させ
、次いで後の重合工程において、極限粘度が少なくとも
５ｄｌ／ｇの高分子量プロピレン重合体（Ｂ）を１５〜
９０重量％生成させる多段階重合法により極限粘度が６
．０〜４０ｄｌ／ｇの範囲の組成物を製造することを特
徴とする超高分子量エチレン重合体組成物の製法。(2) In the presence of a highly stereoregular polymerization catalyst, 10 to 85% by weight of an ultra-high molecular weight ethylene polymer (A) having an intrinsic viscosity of at least 15 dl/g is produced in the first polymerization step, and then in the next polymerization step A high molecular weight propylene polymer (B) having an intrinsic viscosity of at least 5 dl/g is
The intrinsic viscosity is 6 due to the multi-step polymerization method that produces 90% by weight.
．． 1. A method for producing an ultra-high molecular weight ethylene polymer composition, characterized by producing a composition in the range of 0 to 40 dl/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7412187A JPS63241050A (en) | 1987-03-30 | 1987-03-30 | Ultra-high mw ethylene polymer composition and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7412187A JPS63241050A (en) | 1987-03-30 | 1987-03-30 | Ultra-high mw ethylene polymer composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63241050A true JPS63241050A (en) | 1988-10-06 |
Family
ID=13538057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7412187A Pending JPS63241050A (en) | 1987-03-30 | 1987-03-30 | Ultra-high mw ethylene polymer composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63241050A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01156345A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| WO1999015586A1 (en) * | 1997-09-22 | 1999-04-01 | Montell Technology Company B.V. | Polyolefin compositions comprising a propylene polymer and uhmwpe |
| JP2005313391A (en) * | 2004-04-27 | 2005-11-10 | Asahi Kasei Chemicals Corp | Ultra-high molecular weight polyethylene stretch-molded product |
| JP2007023171A (en) * | 2005-07-19 | 2007-02-01 | Mitsui Chemicals Inc | Ultra-high-molecular-weight polyethylene particulate excellent in heat resistance and method for producing the same |
| JP5351178B2 (en) * | 2008-12-26 | 2013-11-27 | 三井化学株式会社 | Ethylene polymer composition, process for producing the same, and molded article obtained using the same |
| WO2018110361A1 (en) * | 2016-12-16 | 2018-06-21 | 東レフィルム加工株式会社 | Release film and protective film |
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- 1987-03-30 JP JP7412187A patent/JPS63241050A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120605A (en) * | 1982-12-28 | 1984-07-12 | Showa Denko Kk | Production of ultrahigh molecular weight polyethylene resin |
| JPS59126446A (en) * | 1983-01-07 | 1984-07-21 | Sekisui Chem Co Ltd | Ultra-high-molecular-weight polyethylene resin composition |
| JPS621736A (en) * | 1985-06-27 | 1987-01-07 | Mitsui Petrochem Ind Ltd | Polyolefin powder composition |
| JPS6310647A (en) * | 1985-06-27 | 1988-01-18 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPS6312606A (en) * | 1986-07-04 | 1988-01-20 | Mitsui Petrochem Ind Ltd | Polyolefin composition for injection molding |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01156345A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| WO1999015586A1 (en) * | 1997-09-22 | 1999-04-01 | Montell Technology Company B.V. | Polyolefin compositions comprising a propylene polymer and uhmwpe |
| US6521709B2 (en) | 1997-09-22 | 2003-02-18 | Basell Poliolefine Italia S.P.A. | Polyolefin compositions comprising a propylene polymer and UHMWPE |
| JP2005313391A (en) * | 2004-04-27 | 2005-11-10 | Asahi Kasei Chemicals Corp | Ultra-high molecular weight polyethylene stretch-molded product |
| JP2007023171A (en) * | 2005-07-19 | 2007-02-01 | Mitsui Chemicals Inc | Ultra-high-molecular-weight polyethylene particulate excellent in heat resistance and method for producing the same |
| JP5351178B2 (en) * | 2008-12-26 | 2013-11-27 | 三井化学株式会社 | Ethylene polymer composition, process for producing the same, and molded article obtained using the same |
| WO2018110361A1 (en) * | 2016-12-16 | 2018-06-21 | 東レフィルム加工株式会社 | Release film and protective film |
| JPWO2018110361A1 (en) * | 2016-12-16 | 2019-10-24 | 東レフィルム加工株式会社 | Release film and protective film |
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