JPH0720898B2 - A method for synthesizing spherical, narrow particle size distribution magnesium alcoholates. - Google Patents
A method for synthesizing spherical, narrow particle size distribution magnesium alcoholates.Info
- Publication number
- JPH0720898B2 JPH0720898B2 JP21017889A JP21017889A JPH0720898B2 JP H0720898 B2 JPH0720898 B2 JP H0720898B2 JP 21017889 A JP21017889 A JP 21017889A JP 21017889 A JP21017889 A JP 21017889A JP H0720898 B2 JPH0720898 B2 JP H0720898B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- alcohol
- particle size
- reaction
- size distribution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011777 magnesium Substances 0.000 title claims description 75
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 71
- 229910052749 magnesium Inorganic materials 0.000 title claims description 67
- 239000002245 particle Substances 0.000 title claims description 58
- 238000009826 distribution Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 19
- 230000002194 synthesizing effect Effects 0.000 title claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- 239000010936 titanium Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- -1 ethylene, propylene Chemical group 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用） 本発明は、α−オレフィン重合触媒用担体、アルコール
等の脱水剤、セラミックス原料などに有用な粒径が10〜
50μｍの球形で粒度分布範囲の狭いマグネシウムアルコ
ラートの合成方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Use] The present invention has a useful particle size of 10 to 10 as a carrier for an α-olefin polymerization catalyst, a dehydrating agent such as alcohol, and a ceramic raw material.
The present invention relates to a method for synthesizing a magnesium alcoholate having a spherical shape of 50 μm and a narrow particle size distribution range.
（従来の技術） α−オレフィン類の重合触媒としてチーグラー（Ziegle
r）触媒が開発され常温常圧でエチレン、プロピレン等
の重合が行なえるようになったことは周知の通りであ
る。このチーグラー型触媒の一成分として固体のチタン
ハロゲン化物が用いられているが、初期のチーグラー型
触媒においては、触媒成分中のチタン当りの重合体収量
が低く、別言すれば、チタン当りの重合活性が低く、触
媒残渣の除去工程（いわゆる脱灰工程）が不可欠であっ
た。これに対し、近年チタンハロゲン化物のうち、三塩
化チタンが活性を有することが見い出され、三塩化チタ
ン型触媒を用いることにより触媒残渣の除去負荷が軽減
されるようになってきている。しかし、この場合でも実
際の活性種となるものは使用総チタンの0.1％以下にす
ぎないと言われている。これは三塩化チタンの固体表面
の極く一部のタチン原子が触媒活性にあずかるだけであ
り、固体内部のチタン原子はまったく触媒活性に寄与し
ないためである。(Prior Art) As a polymerization catalyst for α-olefins (Ziegle
r) It is well known that a catalyst was developed and it became possible to polymerize ethylene, propylene, etc. at normal temperature and pressure. Solid titanium halides are used as one component of this Ziegler type catalyst, but in the early Ziegler type catalysts, the polymer yield per titanium in the catalyst component was low. Since the activity is low, the step of removing the catalyst residue (so-called deashing step) was essential. On the other hand, in recent years, among titanium halides, titanium trichloride has been found to be active, and the use of a titanium trichloride-type catalyst has reduced the catalyst residue removal load. However, even in this case, the actual active species are said to be less than 0.1% of the total titanium used. This is because only a small portion of the tatin atoms on the solid surface of titanium trichloride participates in the catalytic activity, and the titanium atoms inside the solid do not contribute to the catalytic activity at all.
前記したチグラー型触媒におけるチタン当りの低い重合
活性という問題を解決するために、最近においては、マ
グネシウム化合物上に三塩化チタンをコートする方法
（担持型触媒）が開発され、マグネシウム化合物として
塩化マグネシウムが担体として利用されてきている。こ
の担持型触媒により表面積が200m2/gと非常に大きくな
り、例えば、三塩化チタン型触媒に比べ触媒活性が200
倍以上に高活性化される。In order to solve the above-mentioned problem of low polymerization activity per titanium in the Ziegler type catalyst, a method of coating titanium trichloride on a magnesium compound (supported catalyst) has been recently developed, and magnesium chloride is used as the magnesium compound. It has been used as a carrier. This supported catalyst has a very large surface area of 200 m 2 / g.
It is more than twice as highly activated.
前記担持型触媒において、担体として塩化マグネシウム
が選ばれるのは結晶構造の類似性やチタンとマグネシウ
ムのイオン半径の近似性（Mg,0.65Å、Ti,0.68Å）など
のためである。その後、塩化マグネシウムばかりでな
く、Mg（OR）2,RMgX,R2Mgなど種々のマグネシウム化合
物を担体とする担持型触媒による高活性化触媒の開発が
さかんに行なわれている。なかでも、塩化マグネシウム
に含まれる塩素が、生成重合体の劣化や黄変の原因とな
ること、あるいは重合装置を腐蝕させることなどの観点
からマグネシウムアルコラートを用いる担持型触媒に関
する特許が多数提案されている（例えば、特公昭62-474
46号、特公昭64-963号、特開昭59-221308号など。）。In the above-mentioned supported catalyst, magnesium chloride is selected as a carrier because of the similarity in crystal structure and the closeness of ionic radius between titanium and magnesium (Mg, 0.65Å, Ti, 0.68Å). Since then, not only magnesium chloride but also a highly activated catalyst using a supported catalyst having various magnesium compounds such as Mg (OR) 2 , RMgX and R 2 Mg as a carrier has been actively developed. Among them, chlorine contained in magnesium chloride is a cause of deterioration or yellowing of the produced polymer, or from the viewpoint of corroding the polymerization apparatus, many patents on a supported catalyst using magnesium alcoholate have been proposed. (For example, Japanese Patent Publication No. 62-474
No. 46, Japanese Examined Patent Publication No. 64-963, Japanese Unexamined Patent Publication No. 59-221308, etc. ).
また、最近においては、シリカ（SiO2）を担体とするシ
リカ担持型触媒も開発されている。即ち、シリカにMg化
合物やTi化合物を担持させるものが開発されている。Further, recently, a silica-supported catalyst having silica (SiO 2 ) as a carrier has been developed. That is, a silica supporting a Mg compound or a Ti compound has been developed.
一方、担持型触媒による重合反応の特徴は、重合反応生
成物であるポリマーの形状が重合反応の中心となる触媒
の形状、すなわち担体となるマグネシウム化合物の形状
に相似するという点である。このことは、担体となるマ
グネシウム化合物の形状、粒径を制御することにより生
成する重合体の形状、粒径を制御することができること
を意味する。On the other hand, the characteristic of the polymerization reaction by the supported catalyst is that the shape of the polymer which is the polymerization reaction product is similar to the shape of the catalyst which is the center of the polymerization reaction, that is, the shape of the magnesium compound which is the carrier. This means that the shape and particle size of the polymer produced by controlling the shape and particle size of the magnesium compound serving as a carrier can be controlled.
前記した点は、工業的に重要な意味を有しており、生成
重合体が球形かつ粒度分布が狭ければ、造粒工程の省
略、生成重合体の後処理工程への移送、生成重合体の取
扱い等が極めて容易となる。The above-mentioned points have industrial significance, and if the produced polymer is spherical and has a narrow particle size distribution, the granulation step is omitted, the produced polymer is transferred to the post-treatment step, the produced polymer. Is extremely easy to handle.
以上の観点から、粒子の形状、粒径や粒度分布を所望な
ものに制御しうるマグネシウムアルコラートの製造技術
の確立が強く望まれている。From the above viewpoints, there is a strong demand for establishment of a magnesium alcoholate production technique capable of controlling the particle shape, particle size and particle size distribution to a desired value.
現在、触媒用担体としてのマグネシウムアルコラート
は、マグネシウムアルコラートを機械的に粉砕し、粒度
を整えたものが使用されている。しかしながら、このよ
うな機械的粉砕物は個々の粒子形状が破砕状のものとな
り、かつ粒度分布が広いものとなり重合反応に用いたと
き生成重合体の形状が不均一で取扱い上に問題がある。At present, as the magnesium alcoholate as a catalyst carrier, a magnesium alcoholate mechanically pulverized to have a regulated particle size is used. However, such a mechanically pulverized product has a crushed individual particle shape and a wide particle size distribution, and when used in a polymerization reaction, the shape of the polymer produced is not uniform, which is a problem in handling.
一方、前記した機械的粉砕とは別に、球状（粒子状）の
マグネシウムアルコラート（マグネシウムアルコキシ
ド）を製造する技術としては、例えば次のようなものが
提案されている。On the other hand, as a technique for producing spherical (particulate) magnesium alcoholate (magnesium alkoxide) in addition to the above mechanical pulverization, for example, the following technique has been proposed.
（ｉ）Mg（OR）２をＲ′OH中に溶解して溶液を調製し、
次いで所定温度下で噴霧乾燥して固体粒子を得る。次に
該固体粒子をROH中に懸濁し、更に蒸溜により液相から
一般式Mg（OR）２−ａ・（OR′）ａで示される球状粒子
を製造する方法（特開昭62-51633号）。(I) Dissolve Mg (OR) 2 in R'OH to prepare a solution,
Then, it is spray dried at a predetermined temperature to obtain solid particles. Then, the solid particles are suspended in ROH, and then a spherical particle represented by the general formula Mg (OR) 2-a. (OR ') a is produced from the liquid phase by distillation (JP-A-62-51633). ).
（ii）金属Mgとアルコールを活性化剤（例えばヨウ素、
ハロゲン化アルキル、酢酸、ギ酸エステルなど）の存在
下に反応させるに際し、飽和炭化水素（例えばヘキサ
ン、ヘプタンなどの脂肪族あるいは脂環族の炭化水素）
を存在させる方法（特公昭63-4815号）。(Ii) activator of metal Mg and alcohol (eg iodine,
Saturated hydrocarbons (eg, aliphatic or alicyclic hydrocarbons such as hexane and heptane) when reacted in the presence of alkyl halides, acetic acid, formic acid esters, etc.)
To exist (Japanese Patent Publication No. 63-4815).
しかしながら、前記した球状のマグネシウムアルコラー
トの製造技術は、反応操作が煩雑であったり、金属マグ
ネシウムとアルコールとの直接反応ではなく、かつ製造
されるマグネシウムアルコラートの形状、粒径及び粒度
分布を制御するという観点からみて満足のいくものでは
ない。However, the above-described spherical magnesium alcoholate production technique is not complicated in the reaction operation, is not a direct reaction between metal magnesium and alcohol, and controls the shape, particle size and particle size distribution of the produced magnesium alcoholate. From a point of view, it is not satisfactory.
（発明が解決しようとする問題点） 本発明らは、金属マグネシウムとアルコールとの直接反
応によりマグネシウムアルコラートを製造するに際し、
その形状および粒径を制御できる方法を鋭意検討した。
その結果、合成反応時の金属マグネシウムとアルコール
の添加配合量および反応系における両者の反応時間を規
定することにより、球形でかつ粒度分布範囲の狭いマグ
ネシウムアルコラートが合成できることを見い出し、本
発明を完成するに至った。(Problems to be Solved by the Invention) In the production of magnesium alcoholate by direct reaction of metallic magnesium and alcohol,
The method which can control the shape and particle diameter was studied earnestly.
As a result, they have found that spherical magnesium alcoholate having a narrow particle size distribution range can be synthesized by defining the addition amount of metallic magnesium and alcohol during the synthesis reaction and the reaction time of both in the reaction system, and complete the present invention. Came to.
（問題点を解決するための手段） 本発明を概説すれば、本発明は、金属マグネシウムと一
般式ROHで示されるアルコールとを無溶媒かつ触媒の存
在下に直接反応させてマグネシウムアルコラートを合成
する方法において、 （ｉ）金属マグネシウムとアルコールの反応系への最終
添加割合を金属マグネシウム／アルコール（重量比）＝
1/9〜15とし、 （ii）前記最終添加割合の金属マグネシウムとアルコー
ルを、アルコールの還流下の反応系に連続的または断続
的に添加し、５〜80分間に亘り反応させ、 （iii）次いでアルコールの還流下に熟成反応を行なう
こと、 を特徴とする球形で粒度分布の狭いマグネシウムアルラ
ートの合成方法に関するものである。(Means for Solving Problems) The present invention will be summarized. The present invention synthesizes a magnesium alcoholate by directly reacting metallic magnesium with an alcohol represented by the general formula ROH in the absence of a solvent and in the presence of a catalyst. In the method, (i) the final addition ratio of metal magnesium and alcohol to the reaction system is calculated as metal magnesium / alcohol (weight ratio) =
1/9 to 15, (ii) the metal magnesium and alcohol in the final addition ratio are continuously or intermittently added to the reaction system under the reflux of alcohol, and the reaction is carried out for 5 to 80 minutes, (iii) Then, a aging reaction is carried out under reflux of alcohol, and a method for synthesizing spherical magnesium alrate having a narrow particle size distribution is characterized.
以下、本発明の構成を具体的に説明する。The configuration of the present invention will be specifically described below.
本発明の金属マグネシウムと一般式ROHで示されるアル
コールとの直接反応によるマグネシウムアルコラートの
合成方法において、特徴とする点は、反応系に対する金
属マグネシウムとROHとの最終添加割合を規制するとと
もに、両成分の反応系における反応時間を規制している
点である。前記した反応条件が維持されないと、球径で
特に粒径が10〜50μｍの均一なマグネシウムアルコラー
トを製造することができない。In the method of synthesizing magnesium alcoholate by the direct reaction of the metal magnesium of the present invention and the alcohol represented by the general formula ROH, the characteristic point is that the final addition ratio of the metal magnesium and ROH to the reaction system is regulated, and both components are The point is that the reaction time in the reaction system is regulated. If the above reaction conditions are not maintained, it is impossible to produce a uniform magnesium alcoholate having a spherical diameter, particularly a particle diameter of 10 to 50 μm.
本発明で使用する金属マグネシウム成分は、どのような
形状のものでも使用することができるが、反応性の良好
なものがよい。例えば、数十〜数百メッシュ、より具体
的には100メッシュ程度の粉末状の金属マグネシウムが
使用される。このような反応性（活性）の良好なもの
は、後述する反応時間との関連で十分な反応速度を確保
し、均一な粒径のマグネシウムアルコラートを得るうえ
で好ましいものである。金属マグネシウム粒子の反応性
は表面積に比例し、表面積は金属マグネシウム粒子の粒
径が小さいほど大きいことはいうまでもないことであ
る。The metallic magnesium component used in the present invention may have any shape, but is preferably one having good reactivity. For example, powdered metal magnesium having a size of several tens to several hundreds of meshes, more specifically about 100 meshes, is used. Such a good reactivity (activity) is preferable in order to secure a sufficient reaction rate in relation to the reaction time described later and obtain a magnesium alcoholate having a uniform particle size. It goes without saying that the reactivity of the metal magnesium particles is proportional to the surface area, and the smaller the particle size of the metal magnesium particles, the larger the surface area.
本発明で使用する一般式ROHで示されるアルコール成分
も各種のものが使用される。前記一般式において、Ｒは
C1〜C20のアルキル基、シクロアルキル基、アラルキル
基を示す。本発明で使用されるアルコール類としては、
例えばメタノール、エタノール、プロパノール、ブタノ
ール、ヘキシルアルコールなどがあり、なかでもエタノ
ールが好ましく使用される。Various alcohol components represented by the general formula ROH used in the present invention may be used. In the above general formula, R is
Alkyl C 1 -C 20, cycloalkyl group, an aralkyl group shown. As the alcohols used in the present invention,
For example, there are methanol, ethanol, propanol, butanol, hexyl alcohol, etc. Among them, ethanol is preferably used.
本発明の直接反応によるマグネシウムアルコラートの合
成方法において、前記金属マグネシウム成分とアルコー
ル成分の両成分の反応系に対する添加割合が規制され
る。粒径が数十μｍの球形で、かつ粒度分布の狭いマグ
ネシウムアルコラートを製造するには、両者の反応系に
対する最終添加割合は、金属マグネシウム／アルコール
（重量比）＝1/9〜15に規制される。In the method for synthesizing magnesium alcoholate by the direct reaction of the present invention, the addition ratio of both the metal magnesium component and the alcohol component to the reaction system is regulated. In order to produce a magnesium alcoholate having a spherical particle size of several tens of μm and a narrow particle size distribution, the final addition ratio to both reaction systems is regulated to metallic magnesium / alcohol (weight ratio) = 1/9 to 15 It
本発明において、金属マグネシウム１に対するアルコー
ルの最終添加割合が９を下回る場合、反応生成物中の固
体（マグネシウムアルコラート）濃度が高くなり、粒径
の均一性や流動性が失われる。なお、流動性が消失して
くると反応生成物の取り出し等の操作性が悪くなること
はいうまでもないことである。また、15を上回る場合も
粒径と粒度分布を制御できなくなり、不定形の粗大粒子
や微粉が生成し、目的とする球形で粒度分布の狭いマグ
ネシウムアルコラートを得ることができなくなる。In the present invention, when the final addition ratio of the alcohol to the metal magnesium 1 is less than 9, the solid (magnesium alcoholate) concentration in the reaction product becomes high, and the uniformity of particle size and the fluidity are lost. Needless to say, when the fluidity disappears, the operability such as taking out the reaction product is deteriorated. Also, when it exceeds 15, the particle size and particle size distribution cannot be controlled, and irregular coarse particles and fine powder are generated, and it becomes impossible to obtain the target spherical magnesium alcoholate having a narrow particle size distribution.
また本発明において、前記両反応成分の反応系に対する
最終添加割合のほかに、両反応成分の反応系におけるア
ルコール成分の還流下のもとで、両者の反応時間が規制
される。所望の微細な球形（粒径数十μｍ程度）のマグ
ネシウムアルコラートを製造するには、使用するアルコ
ール成分の還流下において前記両成分の最終添加割合を
連続的または断続的に反応系に添加し、一定時間反応さ
せなければならない。本発明において、前記両成分を反
応系へ連続的または継続的に添加するとともに、使用す
るアルコール成分の還流下において、両成分を15〜80分
間を要して反応させなければならない。本発明におい
て、反応時間の規制は、前記した金属マグネシウムとア
ルコールとの応応系に対する最終添加割合の規制と連動
して反応生成物の性状を大きく左右する。反応時間が５
分未満のときは微粉末のものが多く、また80分以上の長
時間の場合は亜球状の粒子は得られずかつ粒度分布が広
いものとなってしまう。Further, in the present invention, in addition to the final addition ratio of both reaction components to the reaction system, the reaction time of both reaction components is regulated under the reflux of the alcohol component in the reaction system. In order to produce a desired fine spherical magnesium alcoholate (particle size of several tens of μm), the final addition ratio of both components is continuously or intermittently added to the reaction system under reflux of the alcohol component to be used, Must react for a certain period of time. In the present invention, both components must be continuously or continuously added to the reaction system, and both components must be reacted for 15 to 80 minutes under reflux of the alcohol component used. In the present invention, the regulation of the reaction time greatly influences the property of the reaction product in conjunction with the regulation of the final addition ratio to the reaction system of metallic magnesium and alcohol. Reaction time is 5
If it is less than a minute, many fine powders are obtained, and if it is a long time of 80 minutes or more, subspherical particles cannot be obtained and the particle size distribution becomes broad.
本発明において、反応系に金属マグネシウムとアルコー
ルを添加する態様は任意のものでよい。例えば、反応の
初期に両成分の最終添加割合よりも金属マグネシウムの
添加割合を多くし、最終的に前記した最終添加割合に到
達させるようにしてもよいことはいうまでもない。例え
ば、反応の初期条件として両成分の初期添加割合を金属
マグネシウム／アルコール（重量比）＝1/15〜25とし、
次いで最終的に1/9〜1/15になるように添加すればよ
い。本発明において、両成分の反応系への添加の態様に
よりマグネシウムアルコラートの粒径を制御することが
できる。なお、粒径の制御は、後述する触媒の使用量、
触媒の反応系への添加の態様によっても行なうことがで
きるが、前記した反応系に対する金属マグネシウムとア
ルコールとの添加の態様により行なう方が確実である。In the present invention, the mode of adding metallic magnesium and alcohol to the reaction system may be arbitrary. For example, it goes without saying that the addition ratio of metallic magnesium may be made higher than the final addition ratio of both components at the initial stage of the reaction so as to finally reach the final addition ratio described above. For example, as an initial condition of the reaction, the initial addition ratio of both components is metallic magnesium / alcohol (weight ratio) = 1/15 to 25,
Then, it may be added so as to be finally 1/9 to 1/15. In the present invention, the particle size of magnesium alcoholate can be controlled by the mode of addition of both components to the reaction system. The particle size is controlled by the amount of the catalyst used, which will be described later.
Although it can be carried out by the mode of addition of the catalyst to the reaction system, it is more sure to be carried out by the mode of addition of magnesium metal and alcohol to the reaction system described above.
本発明において、金属マグネシウム成分とアルコール成
分とを前記のようにして反応させるが、反応系に触媒を
存在させることはいうまでもないことである。In the present invention, the metallic magnesium component and the alcohol component are reacted as described above, but it goes without saying that a catalyst is present in the reaction system.
前記触媒としては、金属マグネシウムからグリニャール
試薬を調製するときに使用されるハロゲン化アルキルな
どがある。例えば、臭化メチル、塩化メチル、臭化エチ
ル、塩化エチルなどのハロゲン化アルキル、塩化マグネ
シウム、塩化アルミニウムなどのハロゲン化金属、マグ
ネシウムエチラート自身、ヨウ素、酢酸エステルなどが
使用される。Examples of the catalyst include alkyl halides used when preparing a Grignard reagent from metallic magnesium. For example, alkyl halides such as methyl bromide, methyl chloride, ethyl bromide and ethyl chloride, metal halides such as magnesium chloride and aluminum chloride, magnesium ethylate itself, iodine and acetic acid ester are used.
前記した触媒は、反応系に種々の態様で添加される。本
発明においては、アルコール成分が反応系に連続的にあ
るいは断続的に添加されるので、該アルコール成分に触
媒を溶解させてアルコール成分とともに反応系に添加し
てもよい。いずれにしても前記触媒を反応系に添加する
態様により、生成するマグネシウムアルコラートの粒径
を制御することができる。即ち、触媒量が多いほど粒径
が大きくなる傾向にある。しかしながら、触媒量が多い
と凝集が起り、少ないと微粉が増え、粒度分布が広くな
る。従って、前述したように、反応系への金属マグネシ
ウムとアルコール成分の添加割合の調整と添加の態様の
仕方による方が粒径を制御しやすい。The above-mentioned catalyst is added to the reaction system in various ways. In the present invention, since the alcohol component is continuously or intermittently added to the reaction system, a catalyst may be dissolved in the alcohol component and added to the reaction system together with the alcohol component. In any case, the particle size of the magnesium alcoholate produced can be controlled by the mode in which the catalyst is added to the reaction system. That is, the larger the amount of catalyst, the larger the particle size tends to be. However, when the amount of catalyst is large, agglomeration occurs, and when it is small, the amount of fine powder increases and the particle size distribution becomes broad. Therefore, as described above, it is easier to control the particle size by adjusting the ratio of addition of the metallic magnesium and the alcohol component to the reaction system and the mode of addition.
前記したように、触媒の存在下に、所定量の金属マグネ
シウムとアルコールを反応系に添加し、該アルコールの
還流下に５〜80分間反応させ、次いで両反応成分の反応
を完結させかつ生成粒子を熟成させるという観点から、
反応系をさらに所定時間、アルコールの還流下に維持す
る。金属マグネシウムとアルコールとの反応は水素の発
生が停止することにより完結されるが、生成粒子の熟成
や経済的観点から、両成分を添加した後、反応系をアル
コールの還流下に数時間〜20時間前後、維持すればよ
い。As described above, in the presence of the catalyst, a predetermined amount of metallic magnesium and alcohol are added to the reaction system, the reaction is carried out under reflux of the alcohol for 5 to 80 minutes, and then the reaction of both reaction components is completed and the produced particles are formed. From the perspective of aging
The reaction system is kept under reflux of alcohol for a further predetermined time. The reaction between the metal magnesium and the alcohol is completed by stopping the generation of hydrogen, but from the standpoint of aging of the produced particles and from the economical point of view, after adding both components, the reaction system is refluxed with the alcohol for several hours to 20 hours. It should be maintained around the time.
（実施例） 以下、本発明を実施例により更に詳しく説明するが、本
発明はこれら実施例のものに限定されない。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１） 積算型ガスメーターをつないだ還留冷却機、的化ロート
をつけた2l三つ口フラスコを十分乾燥、窒素置換後、金
属マグネシウム（−70メッシュ）粉5gと無水エタノール
100g、ヨウ素0.5gを仕込む。次にオイルバスで加熱し、
エタノールの還留温度で反応を開始させる。(Example 1) A 2 liter three-necked flask equipped with a return distillation cooler connected with an integrating gas meter and a chemical funnel was thoroughly dried, and after nitrogen substitution, 5 g of metal magnesium (-70 mesh) powder and absolute ethanol
Charge 100g and 0.5g iodine. Then heat in an oil bath,
The reaction is started at the distillation temperature of ethanol.
反応開始後、Mg2.5g、エタノール25gを５分毎に８回、4
0分間にわたって添加する。なお、添加終了時の最終添
加割合は、金属マグネシウム／エタノール＝1/12であっ
た。添加終了後、10時間加熱還留を続け、反応を完結さ
せる。After starting the reaction, 2.5g Mg, 25g ethanol 8 times every 5 minutes, 4
Add over 0 minutes. The final addition ratio at the end of the addition was magnesium metal / ethanol = 1/12. After the addition is completed, heating and refluxing are continued for 10 hours to complete the reaction.
反応完結後、ロータリーエバポレーターにて乾燥し、粉
体状のマグネシウムエチラート100gを得た。After the reaction was completed, it was dried by a rotary evaporator to obtain 100 g of powdery magnesium ethylate.
得られたマグネシウムエチラートは、光学顕微鏡による
形状観察で、若干表面に凹凸の見られる亜球状の粒子で
あった。粒度分布は、エタノールに塩化リチウムを電解
質として加えた液を媒質に用いたコールターカウンター
法により測定した。測定の結果、平均粒径（体積比）2
1.9μｍで、その粒度分布は、図１（体積比％／累積体
積比％）に示すようにシャープなものであった。The obtained magnesium ethylate was a sub-spherical particle having a slightly uneven surface when observed with an optical microscope. The particle size distribution was measured by the Coulter counter method using a liquid obtained by adding lithium chloride as an electrolyte to ethanol as a medium. Measurement results, average particle size (volume ratio) 2
At 1.9 μm, the particle size distribution was sharp as shown in FIG. 1 (volume ratio% / cumulative volume ratio%).
比較例１ 実施例１と同じ操作で金属マグネシウム粉、エタノール
を５分毎に10回に分割して85分間かけて添加した。Comparative Example 1 By the same operation as in Example 1, magnesium metal powder and ethanol were added every 5 minutes in 10 batches over 85 minutes.
得られたマグネシウムエチラート粉体は、ガラスを割っ
たような不定形粒子で亜球状の粒子は得られなかった。
得られた粒子の平均粒径は28.6μｍでその粒度分布は、
図２のように広いものであった。The obtained magnesium ethylate powder was an amorphous particle like glass was broken, and a subspherical particle was not obtained.
The average particle size of the obtained particles is 28.6 μm, and its particle size distribution is
It was wide as shown in FIG.
実施例２ 実施例１と同様の装置に金属マグネシウム粉5gとエタノ
ール195gおよび塩化マグネシウム0.5gを仕込んだ。これ
をオイルバスで加熱し、エタノール還留下に反応を開始
させた。反応開始後、金属マグネシウム粉5g、エタノー
ル45gを７分毎に９回に分けて加え、50分間で添加を終
了させた。Example 2 The same apparatus as in Example 1 was charged with 5 g of metallic magnesium powder, 195 g of ethanol and 0.5 g of magnesium chloride. This was heated in an oil bath to start the reaction under the reflux of ethanol. After the reaction was started, 5 g of metallic magnesium powder and 45 g of ethanol were added every 9 minutes in 9 batches, and the addition was completed in 50 minutes.
ロータリーエバポレーターで乾燥し、粉状のマグネシウ
ムエチラート約200gを得た。得られた粉は、光学顕微鏡
で観察したところ、粒径が20〜30μｍで球状の粒子から
成っていることが確認された。It was dried by a rotary evaporator to obtain about 200 g of powdery magnesium ethylate. The obtained powder was observed with an optical microscope, and it was confirmed that the powder had a particle size of 20 to 30 μm and was composed of spherical particles.
比較例２ 従来の粉砕によって作られたもの（デナミート・ノーベ
ル社製の粒径500〜1500μｍのマグネシウムエチラート
粉砕品）の粒度分布を第３図に示す。本発明のものは従
来のものと比較して、極めて狭い粒度分布を有している
ことがわかる。Comparative Example 2 FIG. 3 shows the particle size distribution of a product manufactured by conventional crushing (a crushed product of magnesium ethylate having a particle size of 500 to 1500 μm manufactured by Denamate Nobel). It can be seen that the present invention has an extremely narrow particle size distribution as compared with the conventional one.
本発明の金属マグネシウムとアルコールとの直接反応に
よるマグネシウムアルコラートの合成方法により、球形
で粒度分布範囲の狭いものが効率的に製造される。According to the method for synthesizing magnesium alcoholate by direct reaction of metallic magnesium and alcohol of the present invention, spherical one having a narrow particle size distribution range can be efficiently produced.
そして、本発明のマグネシウムアルコラートの合成方法
により製造されるマグネシウムアルコラートは、α−オ
レフィンの重合用触媒、アルコール等の脱水剤・乾燥
剤、セラミックス原料などに有用なものである。The magnesium alcoholate produced by the method for synthesizing magnesium alcoholate of the present invention is useful as a catalyst for the polymerization of α-olefins, dehydrating agents / desiccants such as alcohols, and ceramic raw materials.
第１図は、本発明の実施例１で製造されたマグネシウム
アルコラートの粒度分布である。第２図、は比較例１で
製造されたマグネシウムアルコラートの粒度分布であ
る。第３図は、粉砕型の従来のマグネシウムアルコラー
トの粒度分布である。FIG. 1 is a particle size distribution of magnesium alcoholate produced in Example 1 of the present invention. FIG. 2 is a particle size distribution of the magnesium alcoholate produced in Comparative Example 1. FIG. 3 is a particle size distribution of a conventional pulverized magnesium alcoholate.
Claims (4)
アルコールとを無溶媒かつ触媒の存在下に直接反応させ
てマグネシウムアルコラートを合成する方法において、 （ｉ）金属マグネシウムとアルコールの反応系への最終
添加割合を金属マグネシウム／アルコール（重量比）＝
1/9〜15とし、 （ii）前記最終添加割合の金属マグネシウムとアルコー
ルを、アルコールの還流下の反応系に連続的または断続
的に添加し、５〜80分間に亘り反応させ、 （iii）次いでアルコールの還流下に熟成反応を行なう
こと、 を特徴とする球形で粒度分布の狭いマグネシウムアルコ
ラートの合成方法。1. A method for directly synthesizing magnesium alcoholate by directly reacting metal magnesium with an alcohol represented by the general formula ROH in the presence of a solvent and a catalyst, comprising the steps of: Metal magnesium / alcohol (weight ratio) =
1/9 to 15, (ii) the metal magnesium and alcohol in the final addition ratio are continuously or intermittently added to the reaction system under the reflux of alcohol, and the reaction is carried out for 5 to 80 minutes, (iii) Then, a aging reaction is carried out under reflux of alcohol, which is characterized in that the spherical alcohol has a narrow particle size distribution.
ルキル基、アラルキル基から選ばれたものである請求項
第１項に記載のマグネシウムアルコラートの合成方法。2. The method for synthesizing magnesium alcoholate according to claim 1, wherein R of ROH is selected from a C 1 -C 20 alkyl group, a cycloalkyl group and an aralkyl group.
項第２項に記載のマグネシウムアルコラートの合成方
法。3. The method for synthesizing magnesium alcoholate according to claim 2, wherein the alcohol is ethyl alcohol.
μｍのものである請求項第１項に記載のマグネシウムア
ルコラートの合成方法。4. The particle size of magnesium alcoholate is 10 to 50.
The method for synthesizing magnesium alcoholate according to claim 1, wherein the magnesium alcoholate has a diameter of μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21017889A JPH0720898B2 (en) | 1989-08-16 | 1989-08-16 | A method for synthesizing spherical, narrow particle size distribution magnesium alcoholates. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21017889A JPH0720898B2 (en) | 1989-08-16 | 1989-08-16 | A method for synthesizing spherical, narrow particle size distribution magnesium alcoholates. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0374341A JPH0374341A (en) | 1991-03-28 |
| JPH0720898B2 true JPH0720898B2 (en) | 1995-03-08 |
Family
ID=16585071
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|---|---|---|---|
| JP21017889A Expired - Lifetime JPH0720898B2 (en) | 1989-08-16 | 1989-08-16 | A method for synthesizing spherical, narrow particle size distribution magnesium alcoholates. |
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-
1989
- 1989-08-16 JP JP21017889A patent/JPH0720898B2/en not_active Expired - Lifetime
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| WO2006033512A1 (en) * | 2004-09-23 | 2006-03-30 | Samsung Total Petrochemicals Co., Ltd. | Method of preparation of spherical support for olefin polymerization catalyst |
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| CN102453150A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Carrier of catalyst for olefin polymerization, process for producing the same, solid catalyst component for olefin polymerization, and catalyst for olefin polymerization |
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