JPH04221389A - Production of dialkyl zinc - Google Patents
Production of dialkyl zincInfo
- Publication number
- JPH04221389A JPH04221389A JP40561590A JP40561590A JPH04221389A JP H04221389 A JPH04221389 A JP H04221389A JP 40561590 A JP40561590 A JP 40561590A JP 40561590 A JP40561590 A JP 40561590A JP H04221389 A JPH04221389 A JP H04221389A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- zinc
- zinc chloride
- produced
- hydroxide
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 title abstract description 6
- 239000011701 zinc Substances 0.000 title abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 49
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 23
- 239000011592 zinc chloride Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 5
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 239000007787 solid Substances 0.000 abstract description 13
- 239000000725 suspension Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 229940057995 liquid paraffin Drugs 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- -1 zinc hydroxide Chemical class 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 2
- 239000002245 particle Substances 0.000 abstract 2
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 1
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、有機合成や高分子重合
触媒として重要なアルキル亜鉛の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing alkyl zinc, which is important as a catalyst for organic synthesis and polymerization.
【０００２】0002
【従来技術】アルキル亜鉛を塩化亜鉛とトリアルキルア
ルミニウムから製造する方法は公知である（特公昭３７
−２０２６ ）。この製造方法では、反応槽への原料の
供給のし易さや、反応の進行の調節し易さから、塩化亜
鉛の懸濁液にトリアルキルアルミニウムを少量ずつ添加
する方法が用いられる。この塩化亜鉛は無水のものが用
いられる。[Prior Art] A method for producing alkylzinc from zinc chloride and trialkylaluminium is known (Japanese Patent Publication No. 37
-2026). In this production method, a method is used in which trialkylaluminum is added little by little to a suspension of zinc chloride because of the ease of supplying raw materials to the reaction tank and the ease of controlling the progress of the reaction. Anhydrous zinc chloride is used.
【０００３】0003
【発明が解決しようとする課題】ところが、この反応で
は反応の進行と共に原料の塩化亜鉛とは別に黒色の固体
が副生し、それらが次第に凝集し団粒化して、反応末期
には、直径３ｃｍを越える粘着性の塊を形成し、浮遊す
る現象を起こすことが判った。そしてこの塊は攪拌機に
粘着して攪拌を困難にしたり、蒸留装置への移液を不可
能にするなど製造上重大な困難をもたらすことが明らか
になった。従って、上記反応によりアルキル亜鉛を工業
的に製造するためには、この塊状の副生物の生成を防止
する必要があり、この解決法が要望されていた。[Problem to be solved by the invention] However, as the reaction progresses, black solids are produced as a by-product in addition to the raw material zinc chloride, and these solids gradually aggregate and form granules, and at the end of the reaction, a solid with a diameter of 3 cm is produced. It was found that a sticky mass exceeding 100% was formed, causing a floating phenomenon. It has become clear that these lumps stick to the stirrer, making stirring difficult, and making it impossible to transfer the liquid to the distillation apparatus, causing serious difficulties in production. Therefore, in order to industrially produce alkylzinc by the above reaction, it is necessary to prevent the formation of this lumpy by-product, and a solution to this problem has been desired.
【０００４】0004
【課題を解決するための手段】本発明者らは、上記問題
を解決するため鋭意研究を行った結果、塩化亜鉛の懸濁
液にケイ素の酸化物、アルミニウムの酸化物、アルミニ
ウムの水酸化物、亜鉛の水酸化物の中から１種以上を、
塩化亜鉛の１ｗｔ％以上を前もって添加して後、トリア
ルキルアルミニウムを装入して反応を行う事により驚く
べきことに副生する固体の凝集、団粒化を防止出来るこ
とを発見した。[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors have found that silicon oxide, aluminum oxide, and aluminum hydroxide are added to a suspension of zinc chloride. , one or more types of zinc hydroxide,
It has been surprisingly discovered that by adding 1 wt % or more of zinc chloride in advance and then charging trialkylaluminium and carrying out the reaction, agglomeration and agglomeration of by-product solids can be prevented.
【０００５】又この方法による特別の発熱も生じないし
、収率の低下も起こらない。その結果反応中の攪拌も反
応後の移液も円滑に出来るようになり、上記問題点を一
掃し本発明を完成した。以下、本発明について更に詳し
く説明する。[0005] Furthermore, this method does not generate any particular heat generation and does not cause a decrease in yield. As a result, stirring during the reaction and liquid transfer after the reaction can be carried out smoothly, eliminating the above-mentioned problems and completing the present invention. The present invention will be explained in more detail below.
【０００６】本発明におけるアルキル亜鉛の生成反応は
下記式（化１）で示される。The reaction for producing alkylzinc in the present invention is shown by the following formula (Chemical formula 1).
【０００７】[0007]
【化１】ＺｎＣｌ２＋２Ｒ３Ａｌ→ＺｎＲ２＋２Ｒ２Ａ
ｌＣｌ反応は無水、不活性の雰囲気中で行われる。塩化
亜鉛はどんな製法のものでも良いが、微粉であることが
好ましく、充分に乾燥しておかねばならない。トリアル
キルアルミニウム（Ｒ３Ａｌ）のアルキル基はＣ１〜Ｃ
７のものが用いられ、好ましくは、Ｃ１〜Ｃ６である。[Chemical formula 1] ZnCl2+2R3Al→ZnR2+2R2A
The lCl reaction is carried out in an anhydrous, inert atmosphere. Zinc chloride may be produced by any method, but it is preferably a fine powder and must be sufficiently dried. The alkyl group of trialkylaluminum (R3Al) is C1-C
7 are used, preferably C1 to C6.
【０００８】本反応に適したトリアルキルアルミニウム
の例としては、トリメチルアルミニウム、トリエチルア
ルミニウム、トリ−ｎ− ブチルアルミニウム、トリイ
ソブチルアルミニウム、トリヘキシルアルミニウム、メ
チルジエチルアルミニウム等である。Examples of trialkylaluminum suitable for this reaction include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, methyldiethylaluminum, and the like.
【０００９】反応時トリアルキルアルミニウムは塩化亜
鉛に対する理論量より少し多く用いる。反応溶剤は原料
及び生成物と反応しない炭化水素溶剤であればなんでも
よいが、主生成物であるジアルキル亜鉛を分離して取り
出すためと、出来れば他方の生成物であるジアルキルア
ルミニウムクロライドも取り出したいので高沸点の炭化
水素溶剤例えば、流動パラフィン、ドデカン、デカリン
が好ましい。反応温度は、２０〜１２０ ℃の範囲で良
く、好ましくは３０〜１００ ℃である。あまりに低い
と反応が遅くなるし、余りに高いと生成したジアルキル
亜鉛が分解して収率を低下させる。[0009] Trialkylaluminum is used in a slightly larger amount than the theoretical amount relative to zinc chloride during the reaction. The reaction solvent may be any hydrocarbon solvent as long as it does not react with the raw materials and products, but in order to separate and take out the main product, dialkyl zinc, and if possible, we also want to take out the other product, dialkyl aluminum chloride. High boiling hydrocarbon solvents such as liquid paraffin, dodecane, decalin are preferred. The reaction temperature may be in the range of 20 to 120°C, preferably 30 to 100°C. If it is too low, the reaction will be slow, and if it is too high, the dialkylzinc formed will decompose, reducing the yield.
【００１０】原料の添加順序は、塩化亜鉛を懸濁した溶
剤に、トリアルキルアルミニウムを加えても良いし、又
その逆の操作を行っても良い。しかし、一般には計量が
容易であること、反応を制御し易いこと等の理由により
塩化亜鉛の懸濁液にトリアルキルアルミニウムを徐々に
装入する。Regarding the order of addition of the raw materials, the trialkylaluminum may be added to the solvent in which zinc chloride is suspended, or the reverse operation may be performed. However, in general, trialkylaluminum is gradually added to the zinc chloride suspension for reasons such as ease of metering and control of the reaction.
【００１１】さて、次に本発明の特徴は、上記の反応時
に、特定の化合物を前もって添加し、その存在下に反応
を行うことである。その特定の化合物とは、ケイ素の酸
化物、アルミニウムの酸化物、アルミニウムの水酸化物
、亜鉛の水酸化物である。Next, the feature of the present invention is that a specific compound is added in advance during the above reaction, and the reaction is carried out in the presence of the specific compound. The specific compounds are silicon oxide, aluminum oxide, aluminum hydroxide, and zinc hydroxide.
【００１２】好ましい化合物としては、シリカ、アルミ
ナ、シリカアルミナ、水酸化アルミニウム、等である。
商品名では、ケイソウ土、セライト等である。これらは
充分に乾燥しておく必要がある。しかし、ごく微量の水
分であれば残存しても本発明の効果に影響はしない。Preferred compounds include silica, alumina, silica alumina, aluminum hydroxide, and the like. Product names include diatomaceous earth and celite. These must be thoroughly dried. However, if a very small amount of water remains, it will not affect the effects of the present invention.
【００１３】これらの化合物の添加量は、塩化亜鉛に対
して１ｗｔ％以上であれば良い。しかし余りに多く加え
ても経費がかかるだけであるから上限は１００ ｗｔ％
に止めることが好ましい。[0013] The amount of these compounds added may be 1 wt% or more based on zinc chloride. However, adding too much will only increase costs, so the upper limit is 100 wt%.
It is preferable to stop at
【００１４】好ましい添加方法は、塩化亜鉛を溶剤に懸
濁させる際に添加混合する方法である。その後、トリア
ルキルアルミニウムの装入速度によって反応の進行を制
御しつつ合成反応を行う。そうすることによって、合成
反応時副生する固体は大きさが直径で最大２ｍｍ程度に
止まり、反応後の溶液は流動性が非常に良好で反応時の
攪拌、反応終了後の反応液の移液等の操作に何らの支障
もきたさない。 反応終了後はジアルキル亜鉛は通常蒸
留によって分離、精製される。ジアルキルアルミニウム
クロライドも同様に蒸留により分離、精製される。また
、他の方法たとえば再結晶、錯体形成等によって分離し
ても良い。更には、水酸化アルミニウム、アルミナにし
て利用してもよい。A preferred method of addition is to add and mix zinc chloride while suspending it in a solvent. Thereafter, the synthesis reaction is carried out while the progress of the reaction is controlled by the charging rate of trialkylaluminium. By doing so, the size of the solid by-produced during the synthesis reaction is limited to a maximum diameter of about 2 mm, and the solution after the reaction has very good fluidity, allowing for stirring during the reaction and transfer of the reaction solution after the reaction is completed. It does not cause any hindrance to operations such as. After the reaction is completed, the dialkylzinc is usually separated and purified by distillation. Dialkyl aluminum chloride is similarly separated and purified by distillation. Alternatively, separation may be performed by other methods such as recrystallization, complex formation, etc. Furthermore, it may be used in the form of aluminum hydroxide or alumina.
【００１５】[0015]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、本発明の範囲はそれによって限定されるもの
ではない。EXAMPLES The present invention will now be explained in more detail with reference to Examples, but the scope of the present invention is not limited thereby.
【００１６】実施例１
攪拌機、滴下ロート、温度計、三方コックを装着した３
００ミリリットルガラス製四つ口フラスコに内部を窒素
置換した。Example 1 3 equipped with a stirrer, dropping funnel, thermometer, and three-way cock
The inside of a 00 ml glass four-necked flask was purged with nitrogen.
【００１７】次に脱水した塩化亜鉛４５ｇ（０．３３モ
ル） を脱水した流動パラフィン３６ｇ に懸濁し、更
に乾燥した水酸化亜鉛１．５ｇ（塩化亜鉛の３．３ ｗ
ｔ％）を混合し懸濁させた。そのあと四つ口フラスコに
装入した。次にトリメチルアルミニウム４８．０ｇ（０
．６６６ モル） を滴下ロートから反応温度を２５℃
に保ちつつ２時間かけて滴下した。Next, 45 g (0.33 mol) of dehydrated zinc chloride was suspended in 36 g of dehydrated liquid paraffin, and then 1.5 g (3.3 w of zinc chloride) of dried zinc hydroxide was suspended in 36 g of dehydrated liquid paraffin.
t%) were mixed and suspended. Then, it was charged into a four-necked flask. Next, 48.0 g of trimethylaluminum (0
．． 666 mol) from the dropping funnel at a reaction temperature of 25°C.
The solution was added dropwise over a period of 2 hours while maintaining the temperature.
【００１８】反応を完結させるため滴下終了後３０分間
攪拌を続けた。反応終了後、溶液中に黒色の固体が副生
したが、その大きさは直径で最大１ｍｍ 程であり攪拌
や溶液の抜き出しに何らの支障もなかった。又、溶液を
分析したところ、ジメチル亜鉛の収率は９３％であった
。In order to complete the reaction, stirring was continued for 30 minutes after the completion of the dropwise addition. After the reaction was completed, a black solid formed as a by-product in the solution, but the size of the solid was about 1 mm at most in diameter and did not pose any problem in stirring or extracting the solution. Further, when the solution was analyzed, the yield of dimethylzinc was 93%.
【００１９】実施例２
実施例１と同様の装置と方法を用いて実験を行ったが、
試薬として今回は脱水した塩化亜鉛４７．９ｇ（０．３
５２ モル）流動パラフィン４０ｇ 、アルミナ２ｇ（
塩化亜鉛の４．２ ｗｔ％）の懸濁液とトリ−ｎ−ブチ
ルアルミニウム１４７ｇ（０．７１６ モル） を用い
た。反応終了後、副生した黒色の固体の大きさは直径で
最大１ｍｍであった。Example 2 An experiment was conducted using the same equipment and method as in Example 1, but
As a reagent this time, we used 47.9g (0.3g) of dehydrated zinc chloride.
52 mol) liquid paraffin 40g, alumina 2g (
A suspension of zinc chloride (4.2 wt%) and 147 g (0.716 mol) of tri-n-butylaluminum were used. After the reaction was completed, the black solid by-produced had a maximum diameter of 1 mm.
【００２０】実施例３
実施例１と同様の装置と方法を用いて実験を行ったが、
試薬として今回は脱水した塩化亜鉛 ４５ｇ（０．３３
０ モル）ドデカン４０ｇ 、セライト０．５ｇ（塩化
亜鉛の１．１ ｗｔ％）の懸濁液とトリエチルアルミニ
ウム ７８ｇ（０．６８３ モル）を用いた。Example 3 An experiment was conducted using the same equipment and method as in Example 1, but
As a reagent, we used 45 g of dehydrated zinc chloride (0.33
A suspension of 40 g of dodecane (0 mol), 0.5 g of Celite (1.1 wt% of zinc chloride) and 78 g of triethylaluminum (0.683 mol) was used.
【００２１】反応終了後、副生した黒色の固体の大きさ
は、直径で最大２ｍｍであった。又、溶液を分析したと
ころ、ジエチル亜鉛の収率は９４％であった。[0021] After the reaction was completed, the size of the black solid by-produced was 2 mm at most in diameter. Further, when the solution was analyzed, the yield of diethylzinc was 94%.
【００２２】実施例４
攪拌機、滴下ロート、温度計、三方コックを装置した１
リットルのガラス製四つ口フラスコの内部を窒素置換し
た。次に脱水した塩化亜鉛３００ｇ（２．２ モル）、
乾燥した水酸化アルミニウム６．５ｇ（塩化亜鉛の２．
２ｗｔ％）を流動パラフィン３００ｇに混合し懸濁して
四つ口フラスコに装入した。次にトリエチルアルミニウ
ム５１１ｇ（４．４７モル）を滴下ロートから反応温度
を３５℃に保ちつつ３時間に渡って滴下した。水酸化ア
ルミニウムの存在による特別な発熱は認められなかった
。Example 4 1 equipped with a stirrer, dropping funnel, thermometer, and three-way cock
The inside of a liter glass four-necked flask was purged with nitrogen. Next, 300 g (2.2 mol) of dehydrated zinc chloride,
6.5 g of dry aluminum hydroxide (2.5 g of zinc chloride)
2 wt%) was mixed with 300 g of liquid paraffin, suspended, and charged into a four-necked flask. Next, 511 g (4.47 mol) of triethylaluminum was added dropwise from the dropping funnel over 3 hours while maintaining the reaction temperature at 35°C. No particular exotherm due to the presence of aluminum hydroxide was observed.
【００２３】反応を完結させるため滴下終了後１５分間
攪拌を続けた。反応終了後副生した固体の大きさは直径
で最大２ｍｍであった。攪拌、移液等に何らの問題も生
じなかった。反応液を分析したところ、ジエチル亜鉛の
収率は９０％であった。In order to complete the reaction, stirring was continued for 15 minutes after the completion of the dropwise addition. After the completion of the reaction, the solid by-produced had a maximum diameter of 2 mm. No problems occurred with stirring, liquid transfer, etc. Analysis of the reaction solution revealed that the yield of diethylzinc was 90%.
【００２４】比較例１、２、実施例５、６水酸化アルミ
ニウムの必要添加量の検討を行った。実施例４と同様に
して水酸化アルミニウムの添加量を変えて実験を行った
。結果は表１に示す。これにより添加量は塩化亜鉛の１
ｗｔ％以上であれば良いことがわかる。Comparative Examples 1 and 2, Examples 5 and 6 The necessary amount of aluminum hydroxide to be added was investigated. An experiment was conducted in the same manner as in Example 4, with the amount of aluminum hydroxide added changed. The results are shown in Table 1. As a result, the amount added is 1 of zinc chloride.
It can be seen that it is good if it is at least wt%.
【００２５】[0025]
【表１】[Table 1]
【００２６】[0026]
【発明の効果】本発明の方法によれば、反応時に副生す
る固体の大きさを細かくすることが出来る。その結果反
応中の攪拌時や反応後の反応液の移液を何らの障害も起
こすことなく円滑に行うことができる。又、この方法に
起因する発熱や収率の低下も見られない。その結果、ジ
アルキル亜鉛の製造を容易に行うことが出来る様になり
、産業に利するところ大である。[Effects of the Invention] According to the method of the present invention, it is possible to reduce the size of solids produced by-product during the reaction. As a result, stirring during the reaction and transfer of the reaction solution after the reaction can be carried out smoothly without any hindrance. Furthermore, no heat generation or decrease in yield was observed due to this method. As a result, dialkylzinc can be easily produced, which is of great benefit to industry.
Claims (1)
物、アルミニウムの水酸化物、亜鉛の水酸化物の中から
１種以上を、塩化亜鉛に対し１ｗｔ％以上存在させて、
塩化亜鉛とトリアルキルアルミニウムを反応させること
を特徴とするジアルキル亜鉛の製造方法。1. One or more of silicon oxide, aluminum oxide, aluminum hydroxide, and zinc hydroxide is present in an amount of 1 wt % or more relative to zinc chloride,
A method for producing dialkylzinc, which comprises reacting zinc chloride and trialkylaluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40561590A JP2863321B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing dialkyl zinc |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40561590A JP2863321B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing dialkyl zinc |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04221389A true JPH04221389A (en) | 1992-08-11 |
| JP2863321B2 JP2863321B2 (en) | 1999-03-03 |
Family
ID=18515226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40561590A Expired - Fee Related JP2863321B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing dialkyl zinc |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2863321B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0796859A1 (en) * | 1996-03-19 | 1997-09-24 | Witco GmbH | Stable homogenous formulations of oxidation-sensitive organometallic compounds in paraffines and process for their preparation |
| CN100386330C (en) * | 2006-04-03 | 2008-05-07 | 内蒙古蒙西高新技术集团有限公司 | Process for preparing diethyl zinc |
| CN100408584C (en) * | 2006-06-06 | 2008-08-06 | 大连晶元电子气体研究中心有限公司 | Preparation process of diethyl zinc |
| US8236981B2 (en) | 2008-04-30 | 2012-08-07 | Nippon Aluminum Alkyls, Ltd. | Method for manufacturing dialkylzinc and dialkylaluminum monohalide |
| EP2155759A4 (en) * | 2007-05-07 | 2012-10-17 | Valorisation Rech Soc En Commandite | Methods for preparing diorganozinc compounds |
| CN104774214A (en) * | 2015-04-28 | 2015-07-15 | 河南承明光电新材料股份有限公司 | Preparation method for dimethylzinc |
-
1990
- 1990-12-25 JP JP40561590A patent/JP2863321B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0796859A1 (en) * | 1996-03-19 | 1997-09-24 | Witco GmbH | Stable homogenous formulations of oxidation-sensitive organometallic compounds in paraffines and process for their preparation |
| CN100386330C (en) * | 2006-04-03 | 2008-05-07 | 内蒙古蒙西高新技术集团有限公司 | Process for preparing diethyl zinc |
| CN100408584C (en) * | 2006-06-06 | 2008-08-06 | 大连晶元电子气体研究中心有限公司 | Preparation process of diethyl zinc |
| EP2155759A4 (en) * | 2007-05-07 | 2012-10-17 | Valorisation Rech Soc En Commandite | Methods for preparing diorganozinc compounds |
| US8236981B2 (en) | 2008-04-30 | 2012-08-07 | Nippon Aluminum Alkyls, Ltd. | Method for manufacturing dialkylzinc and dialkylaluminum monohalide |
| CN104774214A (en) * | 2015-04-28 | 2015-07-15 | 河南承明光电新材料股份有限公司 | Preparation method for dimethylzinc |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2863321B2 (en) | 1999-03-03 |
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