JPS6325007B2 - - Google Patents
Info
- Publication number
- JPS6325007B2 JPS6325007B2 JP53101525A JP10152578A JPS6325007B2 JP S6325007 B2 JPS6325007 B2 JP S6325007B2 JP 53101525 A JP53101525 A JP 53101525A JP 10152578 A JP10152578 A JP 10152578A JP S6325007 B2 JPS6325007 B2 JP S6325007B2
- Authority
- JP
- Japan
- Prior art keywords
- filler
- catalyst
- reactor
- polymerization
- solid filler
- 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
Links
- 239000000945 filler Substances 0.000 claims description 111
- 239000003054 catalyst Substances 0.000 claims description 71
- 238000000576 coating method Methods 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 55
- 238000006116 polymerization reaction Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 26
- 150000003623 transition metal compounds Chemical class 0.000 claims description 25
- 239000007791 liquid phase Substances 0.000 claims description 22
- 239000004576 sand Substances 0.000 claims description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000010451 perlite Substances 0.000 claims description 18
- 235000019362 perlite Nutrition 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 230000001413 cellular effect Effects 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 125000002524 organometallic group Chemical group 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- -1 triethylaluminum Chemical compound 0.000 description 61
- 239000002245 particle Substances 0.000 description 57
- 239000004698 Polyethylene Substances 0.000 description 46
- 229920000573 polyethylene Polymers 0.000 description 46
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 37
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 30
- 239000005977 Ethylene Substances 0.000 description 30
- 239000007795 chemical reaction product Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000000178 monomer Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 239000011247 coating layer Substances 0.000 description 14
- 229910001562 pearlite Inorganic materials 0.000 description 14
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000012685 gas phase polymerization Methods 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- 150000003682 vanadium compounds Chemical class 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 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
- 238000009835 boiling Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- AMRCYPCPQPCRDN-UHFFFAOYSA-N chloroperoxy hypochlorite vanadium Chemical compound O(OOCl)Cl.[V] AMRCYPCPQPCRDN-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
Description
【発明の詳細な説明】
この発明は、複合材料、特に、表面にオレフイ
ン重合体コーテイングを有する固体充填剤を製造
する方法に関する。この発明はプラスチツク製品
の製造に利用することができる。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for making composite materials, particularly solid fillers having an olefin polymer coating on their surface. This invention can be used in the production of plastic products.
固体充填剤、たとえば粘土の表面にスチレン、
アクリル酸またはその誘導体のような単量体及び
ラジカル重合開始剤を含む溶液を含潤せしめ、し
かる後放射線または熱重合することによつて固体
充填剤の表面に重合体コーテイングを形成する方
法は知られている（米国特許3661620.Cl.117−
62.2参照）。しかしながら、この方法によつてポ
リオレフインをベースとする重合体のコーテイン
グを形成することはできない。 Solid fillers, such as styrene on the surface of clay,
Methods of forming polymeric coatings on the surface of solid fillers by impregnation with solutions containing monomers such as acrylic acid or derivatives thereof and radical polymerization initiators and subsequent radiation or thermal polymerization are known. (U.S. Patent 3661620.Cl.117−
62.2). However, polyolefin-based polymer coatings cannot be formed by this method.
さらに、固体充填剤の表面には触媒を付着せし
め、この触媒上でエチレンを重合することにより
固体充填剤表面に重合体コーテイングを形成する
方法が知られている。使用する触媒は遷移金属化
合物と有機アルミニウムからなる有機金属錯化合
物触媒である。この方法によれば、たとえばセル
ロースのような固体充填剤とたとえばＮ−ヘプタ
ンのような溶剤を反応容器に入れ、この混合物を
共沸乾燥し、次いで、触媒の第１成分である遷移
金属化合物、たとえば、四塩化バナジウムを上記
混合物に加えることによつて触媒の第１成分を固
体充填剤の表面に液相で付着せしめる。この操作
によつて、触媒成分の一部が充填剤表面に析出す
るが、触媒成分の残部は析出せずに溶剤中に残存
する。次いで、反応器中にエチレンを導入して四
塩化バナジウムを三塩化バナジウムに還元する
が、この還元は充填剤表面と溶剤中とで起こる。
次に触媒の第２成分である有機アルミニウム、た
とえば、トリエチルアルミニウムとエチレンを反
応器中に導入し、エチレンを重合せしめる。エチ
レンの重合は充填剤表面に付着せる触媒上及び溶
剤中に遊離状態で残存する触媒上の両者で起こ
る。この重合は90℃以下の温度及び常圧下に行わ
れる。生成した重合物は洗浄して残留触媒を除去
し、乾燥する（米国特許3503785.Cl.117−62.2参
照）。 Furthermore, a method is known in which a catalyst is attached to the surface of the solid filler and ethylene is polymerized on the catalyst to form a polymer coating on the surface of the solid filler. The catalyst used is an organometallic complex compound catalyst consisting of a transition metal compound and an organoaluminium. According to this method, a solid filler such as cellulose and a solvent such as N-heptane are placed in a reaction vessel, the mixture is azeotropically dried, and then the transition metal compound, which is the first component of the catalyst For example, the first component of the catalyst is deposited in liquid phase on the surface of the solid filler by adding vanadium tetrachloride to the mixture. By this operation, a part of the catalyst component is precipitated on the surface of the filler, but the rest of the catalyst component remains in the solvent without being precipitated. Ethylene is then introduced into the reactor to reduce the vanadium tetrachloride to vanadium trichloride, which occurs at the surface of the filler and in the solvent.
Next, organic aluminum, such as triethylaluminum, which is the second component of the catalyst, and ethylene are introduced into the reactor to polymerize ethylene. Polymerization of ethylene occurs both on the catalyst deposited on the filler surface and on the catalyst remaining free in the solvent. This polymerization is carried out at a temperature below 90° C. and under normal pressure. The resulting polymer is washed to remove residual catalyst and dried (see US Pat. No. 3,503,785.Cl.117-62.2).
上述の方法により得られる反応生成物は意図す
る生成物、すなわち重合体コーテイング層をもつ
充填剤の他にかなり多量のバラスト生成物、すな
わち遊離重合体を含む。このように反応生成物中
に遊離重合体が存在すると、かかる生成物から製
造される製品の機械的強度が低下したり可燃性が
増大するなど製品の品質が低下し、製品の利用分
野が制限される。また、反応生成物中に遊離重合
体が存在することは当初の単量体と触媒を不必要
に多量に消費することになる。たとえば、触媒消
費量は四塩化バナジウムの量で表わして充填剤重
量の0.4〜４重量％に達する。反応生成物から遊
離重合体を完全に除去することは言うに及ばず、
反応生成物中の遊離重合体含有量を低減せしめる
ことも不可能である。 The reaction product obtained by the method described above contains, in addition to the intended product, ie the filler with the polymer coating layer, a considerable amount of the ballast product, ie free polymer. The presence of free polymers in reaction products reduces the quality of products manufactured from such products, such as decreasing the mechanical strength and increasing flammability, and limits the field of application of the products. be done. Also, the presence of free polymer in the reaction product results in unnecessary consumption of initial monomer and catalyst. For example, the catalyst consumption amounts to 0.4 to 4% by weight of the filler weight, expressed in the amount of vanadium tetrachloride. Not to mention the complete removal of free polymer from the reaction product.
It is also not possible to reduce the free polymer content in the reaction product.
上述の方法は充填剤表面に付着形成する重合体
コーテイングの厚さを調整するのが困難な点にお
いても不利である。さらに、充填剤表面に付着し
た重合体は充填剤表面から剥離し易く、そして重
合体コーテイングの厚さが大きくなればなる程こ
の現象は顕著になる。上述の方法は、さらに、最
終反応生成物を洗浄して残留触媒を除去しなけれ
ばならない点でも有利ではない。 The above-described method is also disadvantageous in that it is difficult to control the thickness of the polymer coating that forms on the filler surface. Furthermore, polymers attached to the filler surface tend to peel off from the filler surface, and the greater the thickness of the polymer coating, the more pronounced this phenomenon becomes. The method described above is also disadvantageous in that the final reaction product must be washed to remove residual catalyst.
本発明の第１の目的は、高品質で且つ厚さの調
節可能な重合体コーテイングを固体充填剤表面に
形成する方法を提供するにある。 A first object of the present invention is to provide a method for forming a high quality, tunable thickness polymer coating on a solid filler surface.
本発明の第２の目的は、遊離重合体の生成を回
避し、従つて利用分野の広い重合体コーテイング
層形成充填剤を提供するにある。 A second object of the present invention is to provide a polymer coating layer-forming filler which avoids the formation of free polymers and thus has a wide range of applications.
本発明の第３の目的は、単量体及び触媒の消費
量を実質的に低減することを可能ならしめた重合
体コーテイングの形成方法を提供するにある。 A third object of the invention is to provide a method of forming a polymer coating which makes it possible to substantially reduce the consumption of monomer and catalyst.
本発明の第４の目的は、最終反応生成物を洗浄
して残留触媒を除去する操作が必要でない重合体
コーテイングを形成する方法を提供するにある。 A fourth object of the present invention is to provide a method of forming a polymer coating that does not require washing the final reaction product to remove residual catalyst.
本発明の上述の目的は、次のような重合体コー
テイングを有する固体充填剤を製造する方法によ
つて達成される。すなわち、本発明にかかる方法
は、遷移金属化合物と周期律表第族または第
族金属の有機化合物からなる有機金属錯化合物触
媒を固体充填剤の表面に形成せしめ、次いで、こ
のように固体充填剤表面に形成せる触媒上で温度
50゜〜170℃、圧力１〜60気圧においてオレフイン
を液相または気相において重合することからなる
方法であつて、上記触媒の第１成分である遷移金
属化合物を0.001〜0.1重量％（遷移金属の量とし
て）固体充填剤の表面に気相から析出せしめ、次
いで該遷移金属化合物を固体充填剤の表面上で還
元せしめ、さらに、上記触媒の第２成分である周
期律表第族または第族金属の有機化合物を液
相または気相から析出せしめることによつて上記
有機金属錯化合物触媒を形成することを特徴とす
る。 The above objects of the invention are achieved by a method for producing a solid filler with a polymer coating as follows. That is, in the method according to the present invention, an organometallic complex compound catalyst consisting of a transition metal compound and an organic compound of a group metal or a group metal of the periodic table is formed on the surface of a solid filler, and then the solid filler is temperature on the catalyst formed on the surface
A method comprising polymerizing an olefin in a liquid phase or a gas phase at a temperature of 50° to 170°C and a pressure of 1 to 60 atmospheres, in which 0.001 to 0.1% by weight of a transition metal compound, which is the first component of the catalyst, is ) is precipitated from the gas phase on the surface of the solid filler, and then the transition metal compound is reduced on the surface of the solid filler, and the transition metal compound is further reduced on the surface of the solid filler, and the second component of the catalyst is The method is characterized in that the organometallic complex compound catalyst is formed by precipitating an organic compound of a metal from a liquid phase or a gas phase.
触媒のそれぞれの成分は、オレフインの重合に
先立つて、上述の順序で充填剤表面に析出するこ
とができる。 Each component of the catalyst can be deposited on the filler surface in the order described above prior to polymerization of the olefin.
また、触媒の第１成分である遷移金属化合物を
オレフインの重合に先立つて充填剤表面に析出、
付着せしめ、次いで、触媒の第２成分である周期
律表第族または第族金属の有機化合物を析出
せしめると同時にオレフインの重合を行うことが
できる。 In addition, the transition metal compound, which is the first component of the catalyst, is precipitated on the surface of the filler prior to the polymerization of the olefin.
The polymerization of the olefin can be carried out at the same time as the deposition and then the precipitation of the second component of the catalyst, an organic compound of a group metal or group metal of the periodic table.
本発明方法により得られる重合体コーテイング
は高品質且つ均一で、充填剤表面に良好な接着力
を示し、密度が0.7〜0.95ｇ／cm3であり、その厚
さは最小厚７×10-3g／m2から広い範囲に亘つて
調節することができる。本発明方法によればバラ
スト生成物、すなわち遊離重合体の生成が回避で
き、従つて、重合体コーテイング層をもつ充填剤
からなる最終生成物から製造される製品は機械的
強度が増大し、可燃性が低減するなど優れた特性
を持つ。また、単量体及び触媒の消費量はかなり
低減できる。たとえば、触媒消費量は充填剤重量
に対し0.001〜0.1重量％（遷移金属の量として）
に低減する。さらに、本発明方法は簡易であつ
て、最終生成物を洗浄して残留触媒を除去する操
作も省ける。 The polymer coating obtained by the method of the invention is of high quality and uniform, exhibits good adhesion to the filler surface, has a density of 0.7 to 0.95 g/ cm3 , and has a minimum thickness of 7 x 10 -3 It can be adjusted over a wide range from g/ m2 . The process according to the invention avoids the formation of ballast products, i.e. free polymers, so that the products produced from the final product consisting of a filler with a polymeric coating have increased mechanical strength and are combustible. It has excellent properties such as reduced susceptibility. Also, the consumption of monomers and catalysts can be reduced considerably. For example, catalyst consumption is 0.001-0.1% by weight relative to filler weight (as amount of transition metal)
Reduce to Furthermore, the method of the present invention is simple and eliminates the need for washing the final product to remove residual catalyst.
本発明方法は連続及びバツチ法のいずれで行つ
てもよい。 The method of the present invention may be carried out either continuously or batchwise.
本発明方法で使用するオレフインとしては、エ
チレン、プロピレン、ブテン及びメチルペンテン
などが挙げられる。これらのオレフインは単独で
も、また２以上を組合わせ用いてもよい。 Olefins used in the method of the present invention include ethylene, propylene, butene and methylpentene. These olefins may be used alone or in combination of two or more.
充填剤としては、砂、白亜、タルク、カオリ
ン、酸化アルミニウム、気泡パーライト、グラフ
アイト、ガラスビーズ、金属粉、金属の酸化物及
び塩、並びに鋸屑などが挙げられ、これらの粒度
は約200〜300ミクロンから数センチメートルの範
囲に亘る。充填剤は、ガラス繊維、アスベスト及
びセルロース繊維のような繊維状材料であつても
よく、また金属シートのようなシート状材料であ
つてもよい。その他の形状及び大きさが異なる固
体材料も充填剤として用いることができる。 Fillers include sand, chalk, talc, kaolin, aluminum oxide, cellular perlite, graphite, glass beads, metal powder, metal oxides and salts, and sawdust, with a particle size of about 200-300 Ranges from microns to several centimeters. Fillers may be fibrous materials such as glass fibers, asbestos and cellulose fibers, or sheet materials such as metal sheets. Other solid materials of different shapes and sizes can also be used as fillers.
本発明にかかる重合体コーテイングを形成する
方法をさらに詳細に説明する。 The method of forming the polymer coating according to the present invention will now be described in further detail.
必要に応じて、充填剤は温度100゜〜200℃にお
いて１〜３時間乾燥した後に反応器に入れる。反
応器は前もつて不活性ガスを吹込むか排気してお
く。次に遷移金属化合物と周期律表第族または
第族金属の有機化合物からなる有機金属錯化合
物触媒を充填剤表面に形成する。第１に、たとえ
ば、四塩化バナジウム、オキシ三塩化バナジウ
ム、四塩化チタン、六塩化タングステン及び三塩
化鉄のような遷移金属化合物を析出せしめる。常
態において液体である四塩化バナジウム、オキシ
三塩化バナジウム及び四塩化チタンは次のように
析出せしめる。すなわち、充填剤を含有する反応
器中にこれらの化合物の１種の蒸気を不活性担体
ガス流とともに、または真空下に導入する。その
結果遷移金属は充填剤表面に析出する。析出に際
して、充填剤が分散材料である場合は、好ましく
はこれを撹拌すべきである。撹拌は機械的振動機
または空気圧手段の他、沸謄振動及び重力撹拌な
ど任意の手段により行うことができる。充填剤表
面に析出した遷移金属化合物は、還元すると共に
充填剤表面の水酸基のような官能基と化学反応せ
しめて遷移金属化合物を充填剤表面に結合せしめ
る。使用する充填剤及び遷移金属化合物の種類に
応じて、充填剤表面に付着せる遷移金属化合物の
還元は２つの方法で行うことができる。第１の方
法は熱還元であり、第２の方法はエチレンまたは
周期律表第族または第族金属の有機化合物
（この有機化合物は本発明方法で使用する触媒の
第２成分である）の上記のような還元剤を使用す
る方法である。周期律表第族または第族金属
の有機化合物の蒸気を還元剤として使用する方法
においては触媒の第２成分を析出せしめることに
よつて触媒の第１成分の充填剤表面における還元
固着及び触媒の第２成分の析出形成を兼ねること
ができる。 If necessary, the filler is dried at a temperature of 100 DEG to 200 DEG C. for 1 to 3 hours before being added to the reactor. The reactor is previously blown with inert gas or evacuated. Next, an organometallic complex compound catalyst consisting of a transition metal compound and an organic compound of a Group or Group metal of the periodic table is formed on the surface of the filler. First, transition metal compounds such as vanadium tetrachloride, vanadium oxytrichloride, titanium tetrachloride, tungsten hexachloride and iron trichloride are precipitated. Vanadium tetrachloride, vanadium oxytrichloride, and titanium tetrachloride, which are normally liquid, are precipitated as follows. That is, the vapor of one of these compounds is introduced into the reactor containing the filler together with a stream of inert carrier gas or under vacuum. As a result, transition metals precipitate on the filler surface. During precipitation, if the filler is a dispersed material, it should preferably be stirred. Stirring can be performed by any means such as mechanical vibrator or pneumatic means, boiling vibration and gravity stirring. The transition metal compound deposited on the surface of the filler is reduced and chemically reacted with functional groups such as hydroxyl groups on the surface of the filler, thereby bonding the transition metal compound to the surface of the filler. Depending on the type of filler and transition metal compound used, the reduction of the transition metal compound deposited on the filler surface can be carried out in two ways. The first method is thermal reduction and the second method is the above-mentioned reduction of ethylene or an organic compound of a group or group metal of the periodic table, which organic compound is the second component of the catalyst used in the process of the invention. This method uses a reducing agent such as In the method of using a vapor of an organic compound of a group metal or a group metal of the periodic table as a reducing agent, the second component of the catalyst is precipitated, thereby causing the first component of the catalyst to be reduced and fixed on the surface of the filler, and the catalyst to be removed. It can also serve as the precipitation formation of the second component.
また、常態で固体である三塩化鉄及び六塩化タ
ングステンのような遷移金属化合物は昇華によつ
て充填剤表面に析出することができる。 Additionally, transition metal compounds such as iron trichloride and tungsten hexachloride, which are normally solid, can be deposited on the filler surface by sublimation.
充填剤表面に析出せしめる遷移金属化合物の使
用量は充填剤重量に基き0.001〜0.1重量％（遷移
金属の量として）である。 The amount of transition metal compound precipitated on the surface of the filler is 0.001 to 0.1% by weight (as amount of transition metal) based on the weight of the filler.
充填剤表面に第１触媒成分を析出せしめた後、
ジエチルアルミニウムクロリド、トリエチルアル
ミニウム、トリイソブチルアルミニウム、ジエチ
ル亜鉛及びジエチルマグネシウムのような、周期
律表第族または第族金属の有機化合物を析出
せしめる。この触媒第２成分の析出はオレフイン
重合に先立つてまたは重合と同時に行うことがで
きる。この析出は、重合反応相に依存して気相ま
たは液相で行う。 After depositing the first catalyst component on the surface of the filler,
Organic compounds of Group or Group metals of the Periodic Table are precipitated, such as diethylaluminium chloride, triethylaluminum, triisobutylaluminum, diethylzinc and diethylmagnesium. This precipitation of the second catalyst component can be carried out prior to or simultaneously with the olefin polymerization. This precipitation takes place in the gas phase or in the liquid phase, depending on the polymerization reaction phase.
気相重合に先立つて触媒の第２成分を気相で析
出形成するには、遷移金属化合物が析出せる充填
剤を反応器中に入れた状態で、これに有機金属化
合物の蒸気を不活性ガスの流れとともに導入す
る。充填剤が分散材料である場合は、遷移金属析
出形成の場合について上述したように撹拌しなが
ら有機金属化合物の析出形成を行うべきである。 To precipitate the second component of the catalyst in the gas phase prior to gas phase polymerization, a filler from which the transition metal compound can be precipitated is placed in a reactor, and the vapor of the organometallic compound is introduced into the reactor using an inert gas. It will be introduced along with the flow. If the filler is a dispersed material, the organometallic compound precipitate formation should be carried out with stirring as described above for the transition metal precipitate formation.
前述のように、触媒の第２成分を第１成分の還
元目的で使用した場合は、さらに触媒の第２成分
を析出生成せしめるための特別な操作は不要であ
る。 As mentioned above, when the second component of the catalyst is used for the purpose of reducing the first component, no special operation is required to precipitate the second component of the catalyst.
このように有機金属錯化合物触媒を析出形成せ
しめた充填剤は重合反応器に入れて、この触媒上
で温度50〜170℃、圧力１〜60気圧においてオレ
フインを液相または気相で重合する。重合反応を
行う間、流動床撹拌、重力もしくは振動沸謄撹
拌、または機械的振動機もしくは空気圧手段によ
り撹拌する。 The filler on which the organometallic complex catalyst has been precipitated is placed in a polymerization reactor, and olefin is polymerized on the catalyst at a temperature of 50 DEG to 170 DEG C. and a pressure of 1 to 60 atmospheres in a liquid phase or a gas phase. While carrying out the polymerization reaction, stirring is carried out by fluidized bed stirring, gravity or vibratory boiling stirring, or by mechanical vibrators or pneumatic means.
触媒の第２成分を気相で析出せしめると同時に
オレフインを気相で重合する場合は、遷移金属化
合物を付着せしめた充填剤を気相反応容器中に入
れ、有機金属化合物の蒸気とガス状単量体を重合
反応器中に同時に導入する。この重合反応は上記
と同様に行うことができる。 When precipitating the second component of the catalyst in the gas phase and simultaneously polymerizing the olefin in the gas phase, a filler to which a transition metal compound is attached is placed in a gas phase reaction vessel, and the vapor of the organometallic compound and the gaseous monomer are mixed. polymers are simultaneously introduced into the polymerization reactor. This polymerization reaction can be carried out in the same manner as above.
触媒の第２成分をオレフインの液相重合に先立
つて液相で析出せしめるには、遷移金属化合物が
析出せる充填剤を液相重合反応器中に入れ、この
反応器中にｎ−ヘプタンまたはベンジンのような
有機溶剤を入れ、次いで、ジエチルアルミニウム
クロリド、トリエチルアルミニウム、トリイソブ
チルアルミニウム、ジエチル亜鉛またはジメチル
マグネシウムのような液状有機金属化合物を加
え、充填剤表面に析出せしめる。次いで、単量体
を反応器に入れて上述の有機溶剤に溶解し、そし
て重合せしめる。重合する間撹拌する。この撹拌
は機械的手段によつて、ガス状単量体を吹込むこ
とによつて、または反応混合物を循環せしめるこ
とにより達成することができる。液相反応は温度
50〜100℃、圧力１〜60気圧において行う。 In order to precipitate the second component of the catalyst in the liquid phase prior to the liquid phase polymerization of the olefin, a filler capable of precipitating the transition metal compound is placed in a liquid phase polymerization reactor, and n-heptane or benzine is added to the reactor. Then, a liquid organometallic compound such as diethylaluminum chloride, triethylaluminum, triisobutylaluminum, diethylzinc or dimethylmagnesium is added and deposited on the filler surface. The monomers are then placed in a reactor, dissolved in the above-mentioned organic solvent, and polymerized. Stir during polymerization. This stirring can be achieved by mechanical means, by blowing in gaseous monomer, or by circulating the reaction mixture. Liquid phase reactions depend on temperature
It is carried out at a temperature of 50 to 100°C and a pressure of 1 to 60 atmospheres.
触媒の第２成分の液相析出とオレフインの液相
重合とを同時に行う場合は、遷移金属化合物が析
出せる充填剤を液相反応重合器中に入れ、次い
で、液状単量体の、または単量体と単量体を溶解
しうる有機溶剤とを加える。そして、単量体と溶
剤または単量体のみを加えると同時に反応器中に
液状有機金属化合物を導入する。かくして触媒の
第２成分の析出形成とオレフインの重合とが同時
に行われる。 When the liquid phase precipitation of the second component of the catalyst and the liquid phase polymerization of the olefin are carried out simultaneously, a filler from which the transition metal compound can be precipitated is placed in the liquid phase reaction polymerization vessel, and then the liquid phase polymerization of the liquid monomer or A monomer and an organic solvent capable of dissolving the monomer are added. Then, the liquid organometallic compound is introduced into the reactor at the same time as the monomer and the solvent or only the monomer are added. Precipitate formation of the second component of the catalyst and polymerization of the olefin thus take place simultaneously.
本発明方法の上述のいかなる態様によつても重
合体コーテイングを表面に形成せしめた固体充填
剤が得られる。 Any of the above-described embodiments of the process of the invention results in a solid filler having a polymeric coating formed on its surface.
触媒の第２成分を液相で析出し、且つオレフイ
ンを液相で重合せしめた場合、最終反応生成物は
乾燥しなければならない。重合体コーテイングの
形成をすべて気相で行つた場合には、最終反応生
成物の乾燥は不用である。 If the second component of the catalyst is precipitated in the liquid phase and the olefin is polymerized in the liquid phase, the final reaction product must be dried. If the formation of the polymer coating is carried out entirely in the gas phase, drying of the final reaction product is unnecessary.
充填剤が分散せる材料であるときは、コーテイ
ング層が形成された後まで粒子相互の粘着が起ら
ないような分散状態に保持する。 When the filler is a dispersible material, it is maintained in a dispersed state such that particles do not stick together until after the coating layer is formed.
本発明に従えば、重合体コーテイングの厚さ
は、温度、圧力及び時間のような重合条件を変え
ることにより容易に調節することができる。重合
体コーテイングの厚さは最小厚さ７×10-3ｇ／m2
から広い範囲に亘つて変えることができ、従つて
充填剤と重合体コーテイングとの重量比が広い範
囲に亘つて種々異なる生成物を得ることができ
る。 According to the present invention, the thickness of the polymer coating can be easily adjusted by varying polymerization conditions such as temperature, pressure and time. The minimum thickness of the polymer coating is 7×10 -3 g/m 2
can be varied over a wide range, so that products with different weight ratios of filler and polymer coating can be obtained over a wide range.
本発明方法に従つて重合体コーテイングを形成
せしめる上述の種々の態様の中では、すべての操
作を気相で行う態様が好ましい。気相で行うと簡
易なコーテイングプロセスにより所望の効果が達
成できる。 Among the various embodiments described above for forming polymeric coatings according to the method of the invention, preferred is the embodiment in which all operations are carried out in the gas phase. When carried out in the gas phase, the desired effect can be achieved through a simple coating process.
以下、本発明の理解を一層良好ならしめる為、
好ましい具体例について説明する。 Below, in order to better understand the present invention,
Preferred specific examples will be explained.
実施例 １
粒度25〜50μの酸化アルミニウムを充填剤とし
て用いた。充填剤は120℃において１時間乾燥し
た後、その5.5ｇをドラムドライヤー型の回転金
属反応器に入れた。反応器中を排気して、四塩化
バナジウム蒸気0.006ｇを導入した。四塩化バナ
ジウム蒸気は酸化アルミニウム粒子の表面に析出
し、析出した四塩化バナジウムは還元すると固
相、すなわち三塩化バナジウムとなつて充填剤表
面に固着した。導入した四塩化バナジウムはほぼ
全量が酸化アルミニウム粒子表面に析出した。還
元は温度100℃において行つた。次いで、塩化バ
ナジウムが析出した酸化アルミニウム粒子を上述
と同じ型の反応器に入れ、98℃に保持した。トリ
イソブチルアルミニウム蒸気0.0213ｇを導入し
て、酸化アルミニウム粒子表面に付着せしめた。
次いで、触媒成分が析出した酸化アルミニウム粒
子を含む反応器中にエチレンを圧力10気圧におい
て導入し、温度98℃において撹拌しながら気相重
合を13分間行つた。ポリエチレンの収量は7.2ｇ
であつた。Example 1 Aluminum oxide with a particle size of 25-50μ was used as filler. After drying the filler at 120° C. for 1 hour, 5.5 g of the filler was placed in a rotating metal reactor of the drum dryer type. The reactor was evacuated and 0.006 g of vanadium tetrachloride vapor was introduced. Vanadium tetrachloride vapor precipitated on the surface of the aluminum oxide particles, and when the precipitated vanadium tetrachloride was reduced, it became a solid phase, that is, vanadium trichloride, and was fixed on the surface of the filler. Almost all of the introduced vanadium tetrachloride was deposited on the surface of the aluminum oxide particles. Reduction was carried out at a temperature of 100°C. The aluminum oxide particles with vanadium chloride precipitated thereon were then placed in a reactor of the same type as described above and maintained at 98°C. 0.0213 g of triisobutylaluminum vapor was introduced and deposited on the surface of the aluminum oxide particles.
Next, ethylene was introduced at a pressure of 10 atmospheres into the reactor containing the aluminum oxide particles in which the catalyst component had been precipitated, and gas phase polymerization was carried out for 13 minutes at a temperature of 98° C. with stirring. Yield of polyethylene is 7.2g
It was hot.
最終生成物、すなわちポリエチレンコーテイン
グを持つ酸化アルミニウム粒子を反応器から取出
した。遊離の重合体は実質的に存在しなかつた。
最終反応生成物は酸化アルミニウム43重量％とポ
リエチレン57重量％から成つていた。重合体コー
テイングは高品質で、その密度は0.9ｇ／cm3であ
り、充填剤の全表面に亘つて均一に分布してい
た。このコーテイングは充填剤表面から剥離せ
ず、充填剤表面に対し強い接着力を示した。この
最終生成物から射出成型した成型品は引張強さ
360Kgｆ／cm2を示した。 The final product, aluminum oxide particles with a polyethylene coating, was removed from the reactor. There was virtually no free polymer present.
The final reaction product consisted of 43% by weight aluminum oxide and 57% by weight polyethylene. The polymer coating was of high quality, with a density of 0.9 g/cm 3 and uniformly distributed over the entire surface of the filler. This coating did not peel off from the filler surface and showed strong adhesion to the filler surface. The molded product injection molded from this final product has a tensile strength of
It showed 360Kgf/ cm2 .
実施例 ２
粒度50〜100μの酸化アルミニウムを充填剤と
して用いた。充填剤120℃において１時間乾燥し
た後、その8.64ｇを反応器に入れた。反応器中を
排気して、四塩化バナジウム蒸気0.0009ｇを導入
して充填剤表面に析出せしめた。導入した四塩化
バナジウムはほぼ全量が酸化アルミニウム粒子表
面に析出した。この四塩化バナジウムが析出した
酸化アルミニウム粒子は温度100℃に保持し、次
いで気相重合反応器へ移した。反応器は温度98℃
に保持した。トリイソブチルアルミニウム蒸気
0.0023ｇとエチレンを重合反応器中へ導入した。
エチレンの圧力は44気圧であつた。11分間重合を
行い、ポリエチレン8.3ｇを得た。Example 2 Aluminum oxide with a particle size of 50-100μ was used as filler. After drying the filler at 120° C. for 1 hour, 8.64 g of it was placed in the reactor. The inside of the reactor was evacuated, and 0.0009 g of vanadium tetrachloride vapor was introduced to deposit on the surface of the filler. Almost all of the introduced vanadium tetrachloride was deposited on the surface of the aluminum oxide particles. The aluminum oxide particles on which vanadium tetrachloride was precipitated were kept at a temperature of 100°C, and then transferred to a gas phase polymerization reactor. The temperature of the reactor is 98℃
was held at triisobutylaluminum vapor
0.0023 g and ethylene were introduced into the polymerization reactor.
The pressure of ethylene was 44 atmospheres. Polymerization was carried out for 11 minutes to obtain 8.3 g of polyethylene.
最終反応生成物はポリエチレンコーテイングを
持つ酸化アルミニウム粒子であつて、酸化アルミ
ニウム含有量は51重量％、ポリエチレン含有量は
49重量％であつた。遊離の重合体は実質的に存在
しなかつた。ポリエチレンコーテイングは酸化ア
ルミニウム粒子の全表面に亘つて一様に分布して
いた。コーテイング層の剥離は認められなかつ
た。 The final reaction product is aluminum oxide particles with a polyethylene coating, with an aluminum oxide content of 51% by weight and a polyethylene content of
It was 49% by weight. There was virtually no free polymer present. The polyethylene coating was uniformly distributed over the entire surface of the aluminum oxide particles. No peeling of the coating layer was observed.
実施例 ３
粒度50〜150μの気泡パーライトを温度150℃に
おいて乾燥し、その28ｇを反応器へ入れた。パー
ライト粒子を撹拌しながら四塩化チタン蒸気
0.014ｇと窒素ガスを反応器中へ導入して四塩化
チタンを析出した。導入した四塩化チタンはほぼ
全量がパーライト粒子表面に析出した。次いで、
ジエチルアルミニウムクロリド蒸気0.08ｇと不活
性ガスを反応器中へ導入した。次に触媒成分を付
着せるパーライト粒子を気相重合反応器へ入れ、
エチレンを圧力３気圧において導入した。重合は
温度80℃において90分間行つた。ポリエチレンの
収量は33ｇであつた。Example 3 Cellular perlite with a particle size of 50-150μ was dried at a temperature of 150°C and 28g thereof was placed in a reactor. Titanium tetrachloride vapor while stirring pearlite particles
0.014 g and nitrogen gas were introduced into the reactor to precipitate titanium tetrachloride. Almost all of the introduced titanium tetrachloride was precipitated on the surface of the pearlite particles. Then,
0.08 g of diethylaluminum chloride vapor and an inert gas were introduced into the reactor. Next, the pearlite particles to which the catalyst components are attached are placed in a gas phase polymerization reactor.
Ethylene was introduced at a pressure of 3 atmospheres. Polymerization was carried out at a temperature of 80°C for 90 minutes. The yield of polyethylene was 33g.
最終生成物はポリエチレンコーテイングを持つ
気泡パーライトの粒子であつて、パーライト含有
量は46重量％、ポリエチレン含有量は54重量％で
あつた。遊離の重合体は実質的に存在しなかつ
た。コーテイングはパーライト粒子全面に亘つて
均一に分布しており、粒子から剥離しなかつた。
コーテイング層の厚さは39×10-2ｇ／m2であつ
た。この生成物から成型せる製品の引張強さは
330Kgｆ／cm2であつた。 The final product was particles of cellular perlite with a polyethylene coating, with a perlite content of 46% by weight and a polyethylene content of 54% by weight. There was virtually no free polymer present. The coating was evenly distributed over the entire surface of the pearlite particles and did not peel off from the particles.
The thickness of the coating layer was 39×10 −2 g/m 2 . The tensile strength of the product molded from this product is
It was 330Kgf/ cm2 .
実施例 ４
粒度150〜200μの砂を乾燥し、その4.7ｇを反応
器に入れた。反応器中を排気し、三塩化鉄0.0038
ｇを昇華せしめて砂粒子の表面に析出せしめた。
上記三塩化鉄のほぼ全量が砂粒子表面に析出し
た。次いで、三塩化鉄が析出した充填剤を気相重
合反応器へ移し、温度を70℃に保持した。トリエ
チルアルミニウム蒸気0.0037ｇ及びエチレンを重
合反応器へ導入し圧力40気圧において10分間重合
を行つた。ポリエチレンの収量は0.9ｇであつた。Example 4 Sand with a particle size of 150-200μ was dried and 4.7g thereof was placed in a reactor. Evacuate the reactor and remove iron trichloride 0.0038
g was sublimed and deposited on the surface of the sand particles.
Almost all of the iron trichloride was precipitated on the surface of the sand particles. Next, the filler with precipitated iron trichloride was transferred to a gas phase polymerization reactor, and the temperature was maintained at 70°C. 0.0037 g of triethylaluminum vapor and ethylene were introduced into the polymerization reactor, and polymerization was carried out at a pressure of 40 atmospheres for 10 minutes. The yield of polyethylene was 0.9g.
最終反応生成物はポリエチレンの均一なコーテ
イング層を持つ砂粒子であつて、砂を84重量％、
ポリエチレンを16重量％含有していた。遊離の重
合体は実質的に存在しなかつた。コーテイング層
の剥離は起こらなかつた。 The final reaction product is sand particles with a uniform coating layer of polyethylene, 84% by weight of sand;
It contained 16% by weight of polyethylene. There was virtually no free polymer present. No peeling of the coating layer occurred.
実施例 ５
実施例１と同様に触媒成分を充填剤表面に析出
せしめ、重合を行つた。但し、充填剤として130
℃で乾燥した粒度10〜150μの砂6.27ｇを用いた。
触媒成分としては四塩化バナジウム0.0011ｇとト
リイソブチルアルミニウム0.0046ｇを用いた。四
塩化バナジウムはほぼ全量が砂表面に析出した。
単量体としてはポリプロピレンを圧力４気圧にお
いて供給した。重量は温度92℃において100分間
行つた。ポリプロピレンの収量は1.6ｇであつた。Example 5 In the same manner as in Example 1, a catalyst component was deposited on the surface of the filler and polymerization was carried out. However, as a filler 130
6.27g of sand with a particle size of 10-150μ, dried at °C, was used.
As catalyst components, 0.0011 g of vanadium tetrachloride and 0.0046 g of triisobutylaluminum were used. Almost all of the vanadium tetrachloride was deposited on the sand surface.
As a monomer, polypropylene was supplied at a pressure of 4 atmospheres. The weighing was carried out for 100 minutes at a temperature of 92°C. The yield of polypropylene was 1.6 g.
最終反応生成物はポリプロピレンコーテイング
を持つ砂の粒子であつて、砂80重量％、ポリプロ
ピレン20重量％を含有していた。遊離の重合体は
実質的に存在しなかつた。ポリプロピレンコーテ
イングは充填剤の全表面に亘つて均一に分布して
おり、剥離は認められなかつた。コーテイング層
の密度は0.8ｇ／cm3、厚さは85×10-2ｇ／m2であ
つた。 The final reaction product was sand particles with a polypropylene coating, containing 80% by weight sand and 20% by weight polypropylene. There was virtually no free polymer present. The polypropylene coating was evenly distributed over the entire surface of the filler and no peeling was observed. The coating layer had a density of 0.8 g/cm 3 and a thickness of 85×10 −2 g/m 2 .
実施例 ６
砂９ｇを130℃で乾燥し、反応器中に入れ、流
動床条件下に四塩化バナジウム0.0047ｇを不活性
ガスと共に導入して砂粒子の表面に析出せしめ
た。四塩化バナジウムはほぼ全量が砂粒子表面に
析出した。さらに同様な流動床条件下に、トリイ
ソブチルアルミニウム蒸気0.015ｇを反応器中に
導入した。かくして塩化バナジウムの還元及び充
填剤表面への固着ならびに有機アルミニウムの析
出を同時に行つた。触媒姓分が析出した充填剤は
気相重合反応器へ入れ、温度165℃において30分
間プロピレンを重合した。プロピレンの圧力は５
気圧であつた。ポリプロピレンの収量は1.9ｇで
あつた。Example 6 9 g of sand was dried at 130° C. and placed in a reactor, and 0.0047 g of vanadium tetrachloride was introduced together with an inert gas under fluidized bed conditions to deposit on the surface of the sand particles. Almost all of the vanadium tetrachloride was precipitated on the surface of the sand particles. Additionally, 0.015 g of triisobutylaluminum vapor was introduced into the reactor under similar fluidized bed conditions. In this way, vanadium chloride was reduced and fixed onto the filler surface, and organic aluminum was precipitated at the same time. The filler on which the catalyst component had precipitated was placed in a gas phase polymerization reactor, and propylene was polymerized at a temperature of 165°C for 30 minutes. The pressure of propylene is 5
It was hot due to atmospheric pressure. The yield of polypropylene was 1.9 g.
最終反応生成物はポリプロピレンコーテイング
を持つ砂の粒子であつて、砂82.6重量％及びポリ
プロピレン17.4重量％を含有していた。遊離の重
合体は実質的に存在しなかつた。ポリプロピレン
コーテイングは充填剤粒子の全面一様に分布して
おり、その剥離は認められなかつた。コーテイン
グ層の密度は0.93ｇ／cm3、厚さは70×10-2ｇ／m2
であつた。 The final reaction product was sand particles with a polypropylene coating containing 82.6% by weight sand and 17.4% by weight polypropylene. There was virtually no free polymer present. The filler particles of the polypropylene coating were uniformly distributed over the entire surface, and no peeling was observed. The density of the coating layer is 0.93 g/cm 3 and the thickness is 70×10 -2 g/m 2
It was hot.
実施例 ７
実施例２と同様に充填剤表面への触媒成分の析
出及び重合を行つた。但し、充填剤として直径
9μ、長さ３〜5μのガラス繊維50ｇを用いた。触
媒成分として、四塩化バナジウム0.023ｇ及びジ
イソブチルアルミニウムクロリド0.043ｇを用い
た。四塩化バナジウムはほぼ全量がガラス繊維表
面に析出した。単量体としてエチレンを圧力20気
圧において供給した。重合は98℃において30分間
行い、ポリエチレン21ｇを得た。Example 7 In the same manner as in Example 2, the catalyst component was deposited on the surface of the filler and polymerized. However, as a filler, the diameter
50 g of glass fiber with a diameter of 9μ and a length of 3 to 5μ was used. As catalyst components, 0.023 g of vanadium tetrachloride and 0.043 g of diisobutylaluminum chloride were used. Almost all of the vanadium tetrachloride was deposited on the surface of the glass fiber. Ethylene was fed as a monomer at a pressure of 20 atmospheres. Polymerization was carried out at 98° C. for 30 minutes to obtain 21 g of polyethylene.
最終反応生成物は個々の繊維表面にボリエチレ
ンコーテイングが形成されたガラス繊維であつ
て、ガラス繊維70.5重量％、ポリエチレン29.5重
量％を含有していた。遊離の重合体は実質的に存
在しなかつた。ポリエチレンコーテイングは繊維
の全表面に一様に付着しており、剥離は起こらな
かつた。コーテイング層の密度は0.85ｇ／cm3であ
つた。 The final reaction product was glass fiber with a polyethylene coating formed on the surface of each fiber, and contained 70.5% by weight of glass fiber and 29.5% by weight of polyethylene. There was virtually no free polymer present. The polyethylene coating adhered uniformly to the entire surface of the fibers and no delamination occurred. The density of the coating layer was 0.85 g/cm 3 .
実施例 ８
粒度50〜150μの気泡パーライトを乾燥し、そ
の60ｇを反応器へ入れた。反応器中を排気し、四
塩化バナジウム蒸気0.0048ｇを導入した。四塩化
バナジウムはほぼ全量がパーライト表面に析出し
た。次いで、エチレンを反応器中に導入して、四
塩化バナジウムを三塩化バナジウムに還元すると
ともにバナジウム化合物を充填表面に固着した。
遷移金属化合物が析出したパーライト粒子を気相
重合反応器へ移し、温度50℃に保持した。パーラ
イト粒子を連続的に撹拌しながら、トリイソブチ
ルアルミニウム0.018ｇをエチレンとともに重合
反応器中へ導入した。かくして、充填剤表面への
有機アルミニウム化合物の析出と触媒上でのエチ
レンの重合を同時に行つた。重合は圧力60気圧に
おいて50分間行い、ポリエチレン61ｇを得た。Example 8 Cellular perlite with a particle size of 50-150μ was dried and 60g thereof was placed in a reactor. The reactor was evacuated and 0.0048 g of vanadium tetrachloride vapor was introduced. Almost all of the vanadium tetrachloride was deposited on the pearlite surface. Ethylene was then introduced into the reactor to reduce vanadium tetrachloride to vanadium trichloride and to fix the vanadium compound to the packed surface.
The pearlite particles on which the transition metal compound had precipitated were transferred to a gas phase polymerization reactor and maintained at a temperature of 50°C. While continuously stirring the pearlite particles, 0.018 g of triisobutylaluminum was introduced into the polymerization reactor together with ethylene. In this way, the precipitation of the organoaluminum compound on the surface of the filler and the polymerization of ethylene on the catalyst were performed simultaneously. Polymerization was carried out at a pressure of 60 atmospheres for 50 minutes to obtain 61 g of polyethylene.
最終生成物はポリエチレンコーテイングをもつ
気泡パーライト粒子であつて、気泡パーライト
49.6重量％、ポリエチレン50.4重量％を含有して
いた。遊離の重合体は実質的に存在しなかつた。
ポリエチレンコーテイングは充填剤の全面に均一
に付着しており、剥離は認められなかつた。コー
テイング層の厚さは35×10-2ｇ／m2であつた。こ
の生成物から成型する製品は引張り強さ290Kg
ｆ／cm2を示した。 The final product is cellular perlite particles with a polyethylene coating;
It contained 49.6% by weight and 50.4% by weight of polyethylene. There was virtually no free polymer present.
The polyethylene coating was uniformly adhered to the entire surface of the filler, and no peeling was observed. The thickness of the coating layer was 35×10 −2 g/m 2 . Products molded from this product have a tensile strength of 290Kg.
f/cm 2 was shown.
実施例 ９
粒度20〜50μのグラフアイトを200℃において
２時間乾燥し、その10ｇを反応器へ入れた。反応
器中を排気し、グラフアイト粒子を撹拌しなが
ら、三オキシ塩化バナジウム蒸気0.012ｇを導入
し、さらにトリイソブチルアルミニウム蒸気
0.041ｇを導入した。三オキシ塩化バナジウムは
ほぼ全量がグラフアイト粒子表面に析出した。次
いで、この有機金属錯化合物触媒が析出したグラ
フアイト粒子を気相重合反応器へ移し、エチレン
を導入して圧力１気圧とした。98℃において30分
間気相重合を行い、重合体4.5ｇを得た。Example 9 Graphite with a particle size of 20-50μ was dried at 200°C for 2 hours and 10g thereof was placed in a reactor. The reactor was evacuated, and while stirring the graphite particles, 0.012 g of vanadium trioxychloride vapor was introduced, followed by triisobutylaluminum vapor.
0.041g was introduced. Almost the entire amount of vanadium trioxychloride was precipitated on the surface of the graphite particles. Next, the graphite particles on which the organometallic complex compound catalyst had precipitated were transferred to a gas phase polymerization reactor, and ethylene was introduced thereinto to make the pressure 1 atm. Gas phase polymerization was carried out at 98° C. for 30 minutes to obtain 4.5 g of polymer.
最終反応生成物はポリエチレンコーテイングを
持つグラフアイト粒子であつて、グラフアイト69
重量％、ポリエチレン31重量％を含有していた。
遊離の重合体は実質的に存在しなかつた。ポリエ
チレンコーテイングは充填剤の全面に一様に付着
しており、剥離は起こらなかつた。 The final reaction product is Graphite particles with a polyethylene coating, Graphite 69
% by weight, and contained 31% by weight of polyethylene.
There was virtually no free polymer present. The polyethylene coating adhered uniformly to the entire surface of the filler and no peeling occurred.
実施例 10
実施例１と同様に、充填剤表面への触媒成分の
析出及び重合を行つた。但し、充填剤としてガラ
スビーズ9.3ｇ、触媒成分として四塩化バナジウ
ム0.0056ｇ及びトリイソブチルアルミニウム
0.019ｇを用いた。四塩化バナジウムはほぼ全量
がガラスビーズ表面上に析出した。単量体として
エチレンを圧力21気圧において供給した。重合は
98℃において20分間行い、重合体2.1ｇを得た。Example 10 In the same manner as in Example 1, the catalyst component was deposited on the surface of the filler and polymerized. However, 9.3g of glass beads as a filler, 0.0056g of vanadium tetrachloride and triisobutylaluminum as catalyst components.
0.019g was used. Almost all of the vanadium tetrachloride was deposited on the surface of the glass beads. Ethylene was fed as monomer at a pressure of 21 atmospheres. Polymerization is
The reaction was carried out at 98° C. for 20 minutes to obtain 2.1 g of polymer.
最終反応生成物はポリエチレンコーテイングを
もつガラスビーズであつて、ガラスビーズ81.6重
量％、ポリエチレン18.4重量％から成つていた。
遊離の重合体は実質的に存在しなかつた。ポリエ
チレンコーテイングは充填剤の全表面に一様に付
着しており、剥離は起こらなかつた。 The final reaction product was glass beads with a polyethylene coating, consisting of 81.6% by weight glass beads and 18.4% by weight polyethylene.
There was virtually no free polymer present. The polyethylene coating adhered uniformly to the entire surface of the filler and no peeling occurred.
実施例 11
実施例３と同様に充填剤表面への触媒成分の析
出及び重合を行つた。但し、充填剤として気泡パ
ーライト20ｇ、触媒成分として四塩化チタン
0.015ｇ及びジエチル亜鉛２ｇを用いた。四塩化
チタンはほぼ全量がパーライト表面に析出した。
単量体としてエチレンを圧力４気圧において供給
し、重合は温度70℃において120分間行つた。重
合体収量は12.5ｇであつた。Example 11 The catalyst component was deposited on the surface of the filler and polymerized in the same manner as in Example 3. However, 20g of cellular pearlite is used as a filler, and titanium tetrachloride is used as a catalyst component.
0.015 g and 2 g of diethylzinc were used. Almost all of the titanium tetrachloride was deposited on the pearlite surface.
Ethylene was supplied as a monomer at a pressure of 4 atmospheres, and polymerization was carried out at a temperature of 70° C. for 120 minutes. The polymer yield was 12.5g.
最終反応生成物はポリエチレンコーテイングを
持つ気泡パーライト粒子であつて、気泡パーライ
ト61重量％、ポリエチレン39重量％を含有してい
た、遊離の重合体は実質的に存在しなかつた。ポ
リエチレンコーテイングは充填剤全面に亘つて一
様に付着しており剥離は起こらなかつた。 The final reaction product was cellular perlite particles with a polyethylene coating, containing 61% by weight cellular perlite, 39% by weight polyethylene, and was substantially free of free polymer. The polyethylene coating adhered uniformly over the entire surface of the filler and no peeling occurred.
実施例 12
10×15cmの銅板の表面を脱脂し、四塩化バナジ
ウム蒸気0.023ｇを不活性ガス雰囲気中で導入し
て、上記表面に析出せしめた。四塩化バナジウム
はほぼ全量が銅板表面に析出した。次いでエチレ
ンを導入し、バナジウム化合物を還元して銅板表
面に固着せしめた。次いで、トリエチルアルミニ
ウム蒸気0.061ｇをエチレンと共に導入し、温度
110℃、圧力60気圧において30分間重合を行つた。Example 12 The surface of a 10×15 cm copper plate was degreased, and 0.023 g of vanadium tetrachloride vapor was introduced in an inert gas atmosphere to deposit on the surface. Almost all of the vanadium tetrachloride was deposited on the surface of the copper plate. Next, ethylene was introduced to reduce the vanadium compound and make it adhere to the surface of the copper plate. Next, 0.061 g of triethylaluminum vapor was introduced together with ethylene, and the temperature
Polymerization was carried out at 110°C and 60 atmospheres for 30 minutes.
その結果、ポリエチレンコーテイングが広範全
面に一様に付着した生成物を得た。遊離の重合体
は実質的に存在しなかつた。コーテイング層の密
度は0.95ｇ／cm3、厚さは1.1×103ｇ／m2であつた。
コーテイング層の剥離は認められなかつた。 As a result, a product was obtained in which the polyethylene coating was uniformly adhered over a wide area. There was virtually no free polymer present. The coating layer had a density of 0.95 g/cm 3 and a thickness of 1.1×10 3 g/m 2 .
No peeling of the coating layer was observed.
実施例 13
粒度50〜150μの気泡パーライト40ｇを150℃で
乾燥し、反応器へ入れた。反応器中を排気し、パ
ーライトを撹拌しながら、四塩化バナジウム蒸気
0.025ｇを不活性ガスとともに導入した。四塩化
バナジウムはほぼ全量がパーライト表面に析出し
た。四塩化バナジウムが析出したパーライト粒子
を100℃に加熱して、バナジウム化合物を三塩化
バナジウムに還元した。このバナジウム化合物が
析出したパーライト粒子を液相重合反応器へ移
し、ｎ−ヘプタン0.7、α−ブデン100ｇ及びト
リイソブチルアルミニウム0.1ｇを加えた。撹拌
しながら温度70℃において６時間重合したとこ
ろ、重合体38.3ｇを得た。Example 13 40g of cellular perlite with a particle size of 50-150μ was dried at 150°C and placed in a reactor. Evacuate the reactor and add vanadium tetrachloride vapor while stirring the perlite.
0.025 g was introduced together with inert gas. Almost all of the vanadium tetrachloride was deposited on the pearlite surface. The pearlite particles on which vanadium tetrachloride was precipitated were heated to 100°C to reduce the vanadium compound to vanadium trichloride. The pearlite particles on which the vanadium compound was precipitated were transferred to a liquid phase polymerization reactor, and 0.7 g of n-heptane, 100 g of α-butene, and 0.1 g of triisobutylaluminum were added. Polymerization was carried out at a temperature of 70° C. for 6 hours with stirring, yielding 38.3 g of polymer.
最終反応生成物はポリブテンコーテイングを持
つパーライト粒子であつて、パーライト51重量
％、ポリブテン49重量％からなつていた。遊離の
重合体は実質的に存在しなかつた。ポリブテンコ
ーテイングは充填剤の全面に一様に付着してお
り、剥離は起こらなかつた。 The final reaction product was perlite particles with a polybutene coating, consisting of 51% by weight perlite and 49% by weight polybutene. There was virtually no free polymer present. The polybutene coating adhered uniformly to the entire surface of the filler and no peeling occurred.
実施例 14
気泡パーライトを150℃で乾燥し、その31ｇを
反応器へ入れた。反応器は不活性ガスで洗浄し、
四塩化バナジウム蒸気0.004ｇを不活性ガスとと
もに反応器中へ導入し、続いてエチレンを導入し
た。その結果、充填剤表面に析出した四塩化バナ
ジウムは還元されて三塩化バナジウムとなつた。
導入した四塩化バナジウムはほぼ全量がパーライ
ト表面に析出した。このバナジウム化合物が固着
した充填剤を液相重合反応器へ移し、ベンジン
0.5ｇ及びトリイソブチルアルミニウム0.02ｇを
加えた。次いでエチレンを導入して圧力を60気圧
とし、この気圧に維持したまま温度70℃において
28分間液相重合を行つた。重合後、生成物は乾燥
した。重合体収量は26.1ｇであつた。Example 14 Foamed perlite was dried at 150°C and 31g thereof was placed in a reactor. The reactor was flushed with inert gas and
0.004 g of vanadium tetrachloride vapor was introduced into the reactor along with an inert gas, followed by ethylene. As a result, vanadium tetrachloride deposited on the surface of the filler was reduced to vanadium trichloride.
Almost all of the introduced vanadium tetrachloride was deposited on the pearlite surface. The filler on which this vanadium compound is fixed is transferred to a liquid phase polymerization reactor, and the benzine
0.5 g and 0.02 g of triisobutylaluminum were added. Next, ethylene was introduced to bring the pressure to 60 atmospheres, and while maintaining this pressure, the temperature was 70℃.
Liquid phase polymerization was carried out for 28 minutes. After polymerization, the product was dried. The polymer yield was 26.1 g.
最終反応生成物はポリエチレンコーテイングを
持つ気泡パーライト粒子であつて、パーライト
54.3重量％、ポリエチレン45.7重量％からなつて
いた。遊離の重合体は実質的に存在しなかつた。
ポリエチレンコーテイングは充填剤の全表面に一
様に付着しており、剥離は起こらなかつた。コー
テイング層の密度は0.86ｇ／cm3であつた。 The final reaction product is cellular perlite particles with a polyethylene coating;
It consisted of 54.3% by weight and 45.7% by weight of polyethylene. There was virtually no free polymer present.
The polyethylene coating adhered uniformly to the entire surface of the filler and no peeling occurred. The density of the coating layer was 0.86 g/cm 3 .
実施例 15
実施例14と同様に、充填剤表面への触媒成分の
析出及び重合を行つた。但し、充填剤として微細
に分割せる硫酸バリウム12ｇを用い、触媒成分と
して四塩化バナジウム0.002ｇ及びトリイソブチ
ルアルミニウム0.016ｇを用い、また、ｎ−ヘプ
タン0.1を加えた。四塩化バナジウムはほぼ全
量が硫酸バリウム表面に析出した。単量体として
エチレンを圧力５気圧において供給し、重合は温
度80℃において120分間行つた。重合体収量は
17.9ｇであつた。Example 15 In the same manner as in Example 14, the catalyst component was deposited on the surface of the filler and polymerized. However, 12 g of finely divided barium sulfate was used as a filler, 0.002 g of vanadium tetrachloride and 0.016 g of triisobutylaluminum were used as catalyst components, and 0.1 g of n-heptane was added. Almost all of the vanadium tetrachloride was deposited on the barium sulfate surface. Ethylene was supplied as a monomer at a pressure of 5 atmospheres, and the polymerization was carried out at a temperature of 80° C. for 120 minutes. The polymer yield is
It weighed 17.9g.
最終反応生成物はポリエチレンコーテイングを
もつ硫酸バリウム粒子であつて、硫酸バリウム41
重量％、ポリエチレン59重量％から成つていた。
遊離の重合体は実質的に存在しなかつた。ポリエ
チレンコーテイングは充填剤の全面に一様に付着
しており、剥離は起こらなかつた。 The final reaction product is barium sulfate particles with a polyethylene coating, barium sulfate 41
% by weight, and 59% by weight of polyethylene.
There was virtually no free polymer present. The polyethylene coating adhered uniformly to the entire surface of the filler and no peeling occurred.
実施例 16
粒度150〜200μの砂を120℃で乾燥し、その14.2
ｇを反応器へ入れた。反応器中を排気し、四塩化
バナジウム蒸気0.018ｇを導入した。四塩化バナ
ジウムはほぼ全量が砂表面に析出した。次いでエ
チレンを導入して、バナジウム化合物を完全に砂
粒子表面に還元固着せしめた。この触媒第１成分
が固着した砂粒子を液相重合反応器中へ入れ、ト
リエチルアルミニウム0.056ｇ及び液状プロピレ
ン120ｇを加えた。温度50℃において3.5時間重合
したところ重合体20ｇを得た。Example 16 Sand with a particle size of 150 to 200μ is dried at 120℃, and its 14.2
g was put into the reactor. The reactor was evacuated and 0.018 g of vanadium tetrachloride vapor was introduced. Almost all of the vanadium tetrachloride was deposited on the sand surface. Next, ethylene was introduced to completely reduce and fix the vanadium compound to the surface of the sand particles. The sand particles on which the first catalyst component was fixed were placed in a liquid phase polymerization reactor, and 0.056 g of triethylaluminum and 120 g of liquid propylene were added thereto. Polymerization was carried out at a temperature of 50° C. for 3.5 hours to obtain 20 g of polymer.
最終反応生成物はポリプロピレンコーテイング
を持つ粒子であつて、砂41.5重量％、ポリプロピ
レン58.5重量％から成つていた。遊離の重合体は
実質的に存在しなかつた。ポリプロピレンコーテ
イングは充填剤の全表面に一様に付着しており、
剥離は起こらなかつた。 The final reaction product was particles with a polypropylene coating and consisted of 41.5% by weight sand and 58.5% by weight polypropylene. There was virtually no free polymer present. The polypropylene coating is uniformly applied to the entire surface of the filler,
No peeling occurred.
実施例 17
気泡パーライトを150℃で乾燥し、その34ｇを
反応器へ入れた。六塩化タングステン0.043ｇを
昇華せしめて充填剤表面に析出した。六塩化タン
グステンはほぼ全量がパーライト表面に析出し
た。この触媒第１成分が析出した充填剤を液相重
合反応器へ入れ、ｎ−ヘキサン0.8、トリエチ
ルアルミニウム0.28ｇ及びエチレンを加えた。撹
拌しながら温度98℃、エチレン圧力10気圧におい
て６時間重合し、生成物を乾燥し、重合体6.9ｇ
を得た。Example 17 Foamed perlite was dried at 150°C and 34g thereof was charged into a reactor. 0.043 g of tungsten hexachloride was sublimed and deposited on the surface of the filler. Almost all of the tungsten hexachloride was deposited on the pearlite surface. The filler on which the first catalyst component was precipitated was put into a liquid phase polymerization reactor, and 0.8 g of n-hexane, 0.28 g of triethylaluminum, and ethylene were added. Polymerization was carried out for 6 hours at a temperature of 98°C and an ethylene pressure of 10 atm with stirring, and the product was dried, yielding 6.9 g of polymer.
I got it.
生成物はポリエチレンコーテイングを持つ気泡
パーライト粒子であつて、気泡パーライト83.2重
量％、ポリエチレン16.8重量％から成つていた。
遊離の重合体は実質的に存在しなかつた。ポリエ
チレンコーテイングは充填剤全面に一様に付着し
ており、剥離は起こらなかつた。 The product was cellular perlite particles with a polyethylene coating, consisting of 83.2% by weight cellular perlite and 16.8% by weight polyethylene.
There was virtually no free polymer present. The polyethylene coating adhered uniformly to the entire surface of the filler, and no peeling occurred.
実施例 18
粒度50〜100μの酸化アルミニウムを120〜150
℃で乾燥し、その39.8ｇを反応器へ入れた。反応
器中を排気し、四塩化チタン0.031ｇを温度100℃
において充填剤表面に析出せしめた。四塩化チタ
ンはほぼ全量が酸化アルミニウム表面に析出し
た。次いで反応器を25℃に冷却し、ジメチルマグ
ネシウム0.0873ｇ、ｎ−ヘプタン0.5及びエチ
レンを加えた。撹拌しながら温度80℃、エチレン
圧力５気圧において３時間重合し、生成物を乾燥
し、重合体24.9ｇを得た。Example 18 Aluminum oxide with a particle size of 50-100μ is 120-150
It was dried at ℃ and 39.8g thereof was put into the reactor. Evacuate the reactor and add 0.031 g of titanium tetrachloride to a temperature of 100°C.
was deposited on the surface of the filler. Almost all of the titanium tetrachloride was deposited on the aluminum oxide surface. The reactor was then cooled to 25° C. and 0.0873 g of dimethylmagnesium, 0.5 g of n-heptane and ethylene were added. Polymerization was carried out at a temperature of 80° C. and an ethylene pressure of 5 atm for 3 hours with stirring, and the product was dried to obtain 24.9 g of a polymer.
得られた生成物はポリエチレンコーテイングを
持つ酸化アルミニウム粒子であつて、酸化アルミ
ニウム61.5重量％、ポリエチレン38.5重量％から
成つていた。遊離の重合体は実質的に存在しなか
つた。ポリエチレンコーテイングは充填剤の全面
に一様に付着しており、剥離は起こらなかつた。 The resulting product was aluminum oxide particles with a polyethylene coating and consisted of 61.5% by weight aluminum oxide and 38.5% by weight polyethylene. There was virtually no free polymer present. The polyethylene coating adhered uniformly to the entire surface of the filler and no peeling occurred.
実施例 19
粒度0.1μの酸化鉄を100℃で乾燥し、その12.6
ｇを反応器へ入れた。反応器中を排気し、充填剤
を撹拌しながら、四塩化バナジウム蒸気0.0011ｇ
を不活性ガスとともに導入した。四塩化バナジウ
ムはほぼ全量が酸化鉄表面に析出した。次いでエ
チレンを導入して、充填剤表面に析出したバナジ
ウム化合物を還元固着せしめた。次に充填剤を気
相重合反応器へ移し、ｎ−ヘプタン0.1及びト
リイソブチルアルミニウム0.0053ｇを加え、さら
にエチレンを加えて圧力を1.2気圧とした。温度
80℃において50分間重合を行い、生成物を乾燥
し、重合体1.1ｇを得た。Example 19 Iron oxide with a particle size of 0.1μ was dried at 100℃, and its 12.6
g was put into the reactor. Evacuate the reactor and add 0.0011 g of vanadium tetrachloride vapor while stirring the filler.
was introduced together with an inert gas. Almost all of the vanadium tetrachloride was deposited on the surface of the iron oxide. Next, ethylene was introduced to reduce and fix the vanadium compound deposited on the surface of the filler. Next, the filler was transferred to a gas phase polymerization reactor, and 0.1 g of n-heptane and 0.0053 g of triisobutylaluminum were added, and ethylene was further added to bring the pressure to 1.2 atmospheres. temperature
Polymerization was carried out at 80° C. for 50 minutes, and the product was dried to obtain 1.1 g of polymer.
得られた生成物はポリエチレンコーテイングを
持つ酸化鉄の粒子であつて、酸化鉄92重量％、ポ
リエチレン８重量％から成つていた。遊離の重合
体は実質的に存在しなかつた。粒子相互の粘着は
起こらず、ポリエチレンコーテイングは充填剤の
全表面に一様に付着しており、コーテイング層の
剥離は認められなかつた。 The resulting product was particles of iron oxide with a polyethylene coating and consisted of 92% by weight iron oxide and 8% by weight polyethylene. There was virtually no free polymer present. No adhesion between particles occurred, the polyethylene coating was uniformly adhered to the entire surface of the filler, and no peeling of the coating layer was observed.
Claims (1)
族金属の有機化合物からなる有機金属錯化合物触
媒を固体充填剤の表面に形成せしめ、次いで、こ
のように固体充填剤表面に形成せる触媒上で温度
50゜〜170℃、圧力１〜60気圧においてオレフイン
を液相または気相において重合することからなる
表面に重合体コーテイングを有する固体充填剤を
製造する方法であつて、上記触媒の第１成分であ
る遷移金属化合物を0.001〜0.1重量％（遷移金属
の量として）固体充填剤の表面に気相から析出せ
しめ、次いで、該遷移金属化合物を固体充填剤の
表面上で還元せしめ、さらに、上記触媒の第２成
分である周期律表第族または第族金属の有機
化合物を液相または気相から析出せしめることに
よつて上記有機金属錯化合物触媒を形成すること
を特徴とする、表面に重合体コーテイングを有す
る固体充填剤を製造する方法。 ２ オレフインの重合前にそれぞれの触媒成分を
固体充填剤表面に析出せしめる特許請求の範囲第
１項記載の方法。 ３ 触媒の第１成分である遷移金属化合物をオレ
フインの重合前に固体充填剤の表面に析出せし
め、触媒の第２成分である周期律表第族または
第族金属の有機化合物をオレフインの重合と同
時に析出せしめる特許請求の範囲第１項記載の方
法。 ４ 固体充填剤が酸化アルミニウム、砂、気泡パ
ーライト、グラフアイト、硫酸バリウム、酸化
鉄、ガラス繊維、ガラスビーズまたは鋼である特
許請求の範囲第１〜３項のいずれかに記載の方
法。[Scope of Claims] 1. An organometallic complex compound catalyst consisting of a transition metal compound and an organic compound of a group metal or group metal of the periodic table is formed on the surface of a solid filler, and then, the catalyst is formed on the surface of the solid filler in this way. Temperature on the catalyst to form
A method for producing a solid filler having a polymer coating on its surface, comprising polymerizing an olefin in the liquid phase or gas phase at a temperature of 50° to 170°C and a pressure of 1 to 60 atmospheres, the first component of the catalyst being 0.001 to 0.1% by weight (in terms of amount of transition metal) of a transition metal compound is deposited from the gas phase on the surface of the solid filler, the transition metal compound is then reduced on the surface of the solid filler, and the catalyst A polymer on the surface, characterized in that the organometallic complex compound catalyst is formed by precipitating an organic compound of a group metal of the periodic table, which is the second component of the metal, from the liquid phase or gas phase. A method of producing a solid filler with a coating. 2. The method according to claim 1, wherein the respective catalyst components are precipitated on the surface of the solid filler before the polymerization of the olefin. 3. A transition metal compound, which is the first component of the catalyst, is precipitated on the surface of the solid filler before the polymerization of the olefin, and a transition metal compound, which is the second component of the catalyst, is deposited on the surface of the solid filler. 2. A method according to claim 1, wherein the precipitations are carried out simultaneously. 4. The method according to any one of claims 1 to 3, wherein the solid filler is aluminum oxide, sand, cellular perlite, graphite, barium sulfate, iron oxide, glass fiber, glass beads or steel.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782836892 DE2836892C2 (en) | 1978-08-23 | 1978-08-23 | Process for applying polymeric coatings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5529522A JPS5529522A (en) | 1980-03-01 |
| JPS6325007B2 true JPS6325007B2 (en) | 1988-05-24 |
Family
ID=6047757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10152578A Granted JPS5529522A (en) | 1978-08-23 | 1978-08-22 | Method of forming polymer coating |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5529522A (en) |
| DE (1) | DE2836892C2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258071A (en) * | 1987-05-14 | 1993-11-02 | Glaverbel | Vitreous filler material for a polymeric matrix |
| LU86880A1 (en) * | 1987-05-14 | 1989-01-19 | Glaverbel | GLASS MICROBALLS INTENDED TO BE IN CONTACT WITH POLYMERIZABLE MATERIALS; PROCESS FOR TREATING GLASS MICROBALLS TO MAKE THEM SUITABLE FOR USE AND POLYMERIZATION METHOD USING SUCH MICROBILLES |
| DE3804775A1 (en) * | 1988-02-16 | 1989-08-17 | Schoeller F Jun Gmbh Co Kg | METHOD FOR PRODUCING PIGMENT-PLASTIC CONCENTRATES |
| FI84562C (en) * | 1990-01-16 | 1991-12-27 | Neste Oy | FARING EQUIPMENT FOR THE FRAME STATION OF HETEROGENE CATALYSTATORS. |
| FI87892C (en) * | 1991-07-16 | 1993-03-10 | Neste Oy | METHOD OF FREQUENCY CONTAINER WITH METAL HALF |
| US5370818A (en) * | 1993-05-28 | 1994-12-06 | Potters Industries, Inc. | Free-flowing catalyst coated beads for curing polyester resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495223A (en) * | 1972-04-28 | 1974-01-17 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3503785A (en) * | 1967-11-15 | 1970-03-31 | Nat Lead Co | Process of forming a polyethylene coating using a vanadium compound as the catalyst |
-
1978
- 1978-08-22 JP JP10152578A patent/JPS5529522A/en active Granted
- 1978-08-23 DE DE19782836892 patent/DE2836892C2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495223A (en) * | 1972-04-28 | 1974-01-17 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5529522A (en) | 1980-03-01 |
| DE2836892A1 (en) | 1980-03-27 |
| DE2836892C2 (en) | 1983-12-01 |
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