JP2022012373A - Method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxy disiloxane - Google Patents
Method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxy disiloxane Download PDFInfo
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- NNQOCEJDAXBGGX-UHFFFAOYSA-N hydroxy-[hydroxy-bis[(2-methylpropan-2-yl)oxy]silyl]oxy-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](O)(OC(C)(C)C)O[Si](O)(OC(C)(C)C)OC(C)(C)C NNQOCEJDAXBGGX-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- OPARTXXEFXPWJL-UHFFFAOYSA-N [acetyloxy-bis[(2-methylpropan-2-yl)oxy]silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)(C)C)OC(C)(C)C OPARTXXEFXPWJL-UHFFFAOYSA-N 0.000 claims abstract description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 33
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- 239000012024 dehydrating agents Substances 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000013078 crystal Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- HORSPSPNXPFOMT-UHFFFAOYSA-N butoxy(silyloxy)silane Chemical compound C(CCC)O[SiH2]O[SiH3] HORSPSPNXPFOMT-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Chemical class 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- -1 siloxane compounds Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QHAHOIWVGZZELU-UHFFFAOYSA-N trichloro(trichlorosilyloxy)silane Chemical compound Cl[Si](Cl)(Cl)O[Si](Cl)(Cl)Cl QHAHOIWVGZZELU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
Description
本発明は、１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの製造方法に関する。 The present invention relates to a method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane.
１，３－ジヒドロキシ－１，１，３，３－テトラアルコキシジシロキサンは高度に制御された分子構造を持つため、シリコーンレジンや接着性を付与するためのシロキサン化合物を精密合成する際の原料として有用である。 Since 1,3-dihydroxy-1,1,3,3-tetraalkoxydisiloxane has a highly controlled molecular structure, it can be used as a raw material for precision synthesis of silicone resins and siloxane compounds for imparting adhesiveness. It is useful.
これまでにヘキサクロロジシロキサンを原料とする合成法が知られているが、この原料は加水分解性が極めて高いために取り扱いが難しく、また、高価であることが難点であった。１，３－ジヒドロキシ－１，１，３，３－テトラアルコキシジシロキサンを工業的に合成して応用していくことを考慮すると、より取り扱いが容易、かつ比較的安価であるアルコキシシランを出発原料とすることが望ましい。 So far, a synthetic method using hexachlorodisiloxane as a raw material has been known, but this raw material has a drawback that it is difficult to handle due to its extremely high hydrolyzability and is expensive. Considering that 1,3-dihydroxy-1,1,3,3-tetraalkoxydisiloxane will be industrially synthesized and applied, alkoxysilane, which is easier to handle and relatively inexpensive, is used as a starting material. Is desirable.
しかし、アルコキシシランが加水分解することで生成するシラノール基は、縮合性が高く、２分子のシラノール基、あるいは１分子のシラノール基およびアルコキシシリル基からシロキサン結合を連続的に生成し得る。このため、目的とする１，３－ジヒドロキシ－１，１，３，３－テトラアルコキシジシロキサンを合成する際、ダイマー化に留まらずにオリゴマー化やポリマー化まで進行してしまう。そのためアルコキシシランを出発原料とする際の縮合反応を制御し、１，３－ジヒドロキシ－１，１，３，３－テトラアルコキシジシロキサンを選択的に合成して単離することは困難であった。 However, the silanol group produced by hydrolysis of alkoxysilane has high condensability and can continuously form a siloxane bond from two molecules of silanol group or one molecule of silanol group and alkoxysilyl group. Therefore, when synthesizing the target 1,3-dihydroxy-1,1,3,3-tetraalkoxydisiloxane, not only dimerization but also oligomerization and polymerization proceed. Therefore, it was difficult to control the condensation reaction when using alkoxysilane as a starting material and selectively synthesize and isolate 1,3-dihydroxy-1,1,3,3-tetraalkoxydisiloxane. ..
本発明は上記事情に鑑みなされたもので、１，３－ジヒドロキシ－１，１，３，３－テトラアルコキシジシロキサンの中でも１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの簡便な合成法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and among 1,3-dihydroxy-1,1,3,3-tetraalkoxydisiloxane, 1,3-dihydroxy-1,1,3,3-tetra-tert- It is an object of the present invention to provide a simple method for synthesizing butoxydisiloxane.
上記課題を解決するため、本発明では、
１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの製造方法であって、ジアセトキシジ‐ｔｅｒｔ－ブトキシシランと、水酸化ナトリウムおよび水酸化カリウムから選ばれる１種以上とを混合して反応させて１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンを製造する製造方法を提供する。
In order to solve the above problems, the present invention
A method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane, which comprises one or more selected from diacetoxydi-tert-butoxysilane, sodium hydroxide and potassium hydroxide. To provide a production method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane by mixing and reacting with each other.
このような製造方法であれば、アルコキシシランを出発原料とし、１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンを簡便な方法で選択的に得ることができる。 With such a production method, 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane can be selectively obtained by a simple method using alkoxysilane as a starting material.
このとき、反応時に、更に脱水剤を混合して反応させることが好ましい。 At this time, it is preferable to further mix and react the dehydrating agent at the time of the reaction.
脱水剤の存在下で上記反応を行う事により、より反応効率を向上させることができる。 By performing the above reaction in the presence of a dehydrating agent, the reaction efficiency can be further improved.
またこのとき、前記脱水剤を、硫酸ナトリウムおよび硫酸マグネシウムから選ばれる１種以上とすることが好ましい。 At this time, it is preferable that the dehydrating agent is one or more selected from sodium sulfate and magnesium sulfate.
このようなものとすれば、本発明の効果をより一層向上させることができる。 If this is the case, the effect of the present invention can be further improved.
またこのとき、反応時に、更に有機溶剤を混合して反応させることが好ましい。 At this time, it is preferable to further mix and react with an organic solvent at the time of the reaction.
有機溶剤の存在下で上記反応を行う事により、より反応効率を向上させることができる。 By carrying out the above reaction in the presence of an organic solvent, the reaction efficiency can be further improved.
またこのとき、前記有機溶剤を、ペンタンおよびヘキサンから選ばれる１種以上とすることが好ましい。 At this time, it is preferable that the organic solvent is one or more selected from pentane and hexane.
このようなものとすれば、本発明の効果をより一層向上させることができる。 If this is the case, the effect of the present invention can be further improved.
以上のように、本発明の製造方法であれば、アルコキシシランを出発原料とし、１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンを簡便な方法で選択的に得ることができる。得られたジシロキサンは、シリコーンレジンや接着性を付与するシロキサン成分を精密合成する際の原料として有用である。 As described above, in the production method of the present invention, alkoxysilane is used as a starting material, and 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane is selectively used by a simple method. Obtainable. The obtained disiloxane is useful as a raw material for precision synthesis of a silicone resin and a siloxane component that imparts adhesiveness.
上述のように、１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの効率的な製造方法が求められていた。 As described above, an efficient method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane has been required.
本発明者らは、上記目的を達成するため鋭意検討を重ねた結果、ジアセトキシジ－ｔｅｒｔ－ブトキシシランならびに水酸化ナトリウムおよび水酸化カリウムから選ばれる１種以上とを混合し反応させることで、ダイマー化が選択的に進行し、１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンが効率的に得られることを見出し、本発明を完成させた。 As a result of diligent studies to achieve the above object, the present inventors mixed and reacted diacetoxydi-tert-butoxysilane and one or more selected from sodium hydroxide and potassium hydroxide to form a dimer. , And found that 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane can be efficiently obtained, and completed the present invention.
即ち、本発明は、
１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの製造方法であって、ジアセトキシジ‐ｔｅｒｔ－ブトキシシランと、水酸化ナトリウムおよび水酸化カリウムから選ばれる１種以上とを混合して反応させて１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンを製造することを特徴とする製造方法である。
A method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane, which comprises one or more selected from diacetoxydi-tert-butoxysilane, sodium hydroxide and potassium hydroxide. Is a production method characterized by producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane by mixing and reacting with each other.
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
本発明の１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの製造方法において、ジアセトキシジ‐ｔｅｒｔ－ブトキシシランが原料として用いられる。 In the method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane of the present invention, diacetoxydi-tert-butoxysilane is used as a raw material.
アセトキシ基は良好な脱離基であり、ヒドロキシ基へ置換されてダイマー化が進行する。アセトキシ基以外のカルボキシ基も、本反応に適用することができると考えられるが、取り扱いおよびコスト的観点から、アセトキシ基が最も良い。ｔｅｒｔ－ブトキシ基も脱離基として働き得るが、立体障害が高いため、水やシラノール基の求核置換反応の進行を抑え、シロキサンオリゴマーやポリマーの生成を防ぐ。 The acetoxy group is a good leaving group and is substituted with a hydroxy group to promote dimerization. It is considered that a carboxy group other than the acetoxy group can be applied to this reaction, but the acetoxy group is the best from the viewpoint of handling and cost. The tert-butoxy group can also act as a leaving group, but since it has high steric hindrance, it suppresses the progress of the nucleophilic substitution reaction of water or silanol groups and prevents the formation of siloxane oligomers and polymers.
本発明の製造方法において、水酸化ナトリウムおよび水酸化カリウムから選ばれる１種以上を添加することにより、脱離したアセトキシ基を、酢酸ナトリウム又は酢酸カリウムの形で析出させることにより反応系中から除去することができる。より収率を高めることができる点から水酸化ナトリウムが好ましい。 In the production method of the present invention, the desorbed acetoxy group is removed from the reaction system by precipitating it in the form of sodium acetate or potassium acetate by adding one or more selected from sodium hydroxide and potassium hydroxide. can do. Sodium hydroxide is preferable because the yield can be further increased.
水酸化ナトリウムおよび水酸化カリウムの添加量の合計は、ジアセトキシジ－ｔｅｒｔ－ブトキシシランに対して２．０～２．２モル当量となる量が好ましく、より好ましくは２．０～２．０５モル当量となる量である。このような範囲内であれば、未反応のジアセトキシジ－ｔｅｒｔ－ブトキシシランが残存することを抑え、かつ、ジアセトキシジ－ｔｅｒｔ－ブトキシシランの過剰な重合反応を抑えることができる。 The total amount of sodium hydroxide and potassium hydroxide added is preferably 2.0 to 2.2 molar equivalents, more preferably 2.0 to 2.05 molar equivalents, relative to diacetoxydi-tert-butoxysilane. Is the amount that becomes. Within such a range, the unreacted diacetoxydi-tert-butoxysilane can be suppressed from remaining, and the excessive polymerization reaction of diacetoxydi-tert-butoxysilane can be suppressed.
反応温度は特に限定されず、室温で行う事ができるが、副反応を抑制する点から、－１０℃～０℃で反応を行う事が好ましい。 The reaction temperature is not particularly limited and can be carried out at room temperature, but it is preferable to carry out the reaction at −10 ° C. to 0 ° C. from the viewpoint of suppressing side reactions.
反応時間は、反応温度及び反応の進行に応じて適宜変更すればよく、１時間～２４時間が好ましい。 The reaction time may be appropriately changed according to the reaction temperature and the progress of the reaction, preferably 1 hour to 24 hours.
本発明の製造方法において、反応系に更に脱水剤を添加してもよい。 In the production method of the present invention, a dehydrating agent may be further added to the reaction system.
脱水剤は反応にて生じる水分子をトラップし、ｔｅｒｔ－ブトキシ基の加水分解縮合によるシロキサンオリゴマーやポリマーの生成を防ぐ。 The dehydrating agent traps water molecules generated in the reaction and prevents the formation of siloxane oligomers and polymers due to the hydrolysis condensation of tert-butoxy groups.
脱水剤としては、硫酸ナトリウム、硫酸マグネシウム、塩化カルシウム等の塩が挙げられ、これらの中でも硫酸ナトリウム、硫酸マグネシウムが好ましい。 Examples of the dehydrating agent include salts of sodium sulfate, magnesium sulfate, calcium chloride and the like, and among these, sodium sulfate and magnesium sulfate are preferable.
これらの塩を脱水剤として用いる場合の添加量は、ジアセトキシジ－ｔｅｒｔ－ブトキシシランに対して１．０～５．０モル当量となる量が好ましく、より好ましくは１．０～３．０モル当量となる量である。このような範囲内であれば、反応系中での混合攪拌を阻害することなく、発生した水を速やかに脱水する。 When these salts are used as a dehydrating agent, the amount added is preferably 1.0 to 5.0 molar equivalents with respect to diacetoxydi-tert-butoxysilane, and more preferably 1.0 to 3.0 molar equivalents. Is the amount that becomes. Within such a range, the generated water is quickly dehydrated without disturbing the mixing and stirring in the reaction system.
また、脱水剤として、シリカゲル、ゼオライト等の多孔質吸着剤を用いることもできる。多孔質吸着剤の使用量は、ジアセトキシジ－ｔｅｒｔ－ブトキシシラン１質量部に対して１～１０質量部となる量が好ましく、より好ましくは１～５質量部となる量である。このような範囲内であれば、反応系中での混合攪拌を阻害することなく、発生した水を速やかに除くことができる。 Further, as the dehydrating agent, a porous adsorbent such as silica gel or zeolite can also be used. The amount of the porous adsorbent used is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 1 part by mass of diacetoxydi-tert-butoxysilane. Within such a range, the generated water can be quickly removed without disturbing the mixing and stirring in the reaction system.
また、本発明の製造方法において、反応の際に攪拌効率を向上させる目的で有機溶剤を添加してもよい。 Further, in the production method of the present invention, an organic solvent may be added for the purpose of improving the stirring efficiency during the reaction.
有機溶剤の具体的としてはペンタン、ヘキサン、テトラヒドロフラン、ベンゼン、トルエン、キシレン等が挙げられ、中でも吸湿性の低さからペンタン、ヘキサンが好適である。 Specific examples of the organic solvent include pentane, hexane, tetrahydrofuran, benzene, toluene, xylene and the like, and among them, pentane and hexane are preferable because of their low hygroscopicity.
有機溶剤の使用量は、ジアセトキシジ－ｔｅｒｔ－ブトキシシラン１質量部に対して５～１００質量部となる量が好ましく、より好ましくは１０～６０質量部となる量である。 The amount of the organic solvent used is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass with respect to 1 part by mass of diacetoxydi-tert-butoxysilane.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
［実施例１］
不活性雰囲気下にて、三口フラスコにジアセトキシジ－ｔｅｒｔ－ブトキシシラン（信越化学工業株式会社製）０．３１ｇ及びヘキサン１０ｍｌを加え、０℃に冷却した。そこへ水酸化ナトリウム（富士フイルム和光純薬株式会社製）０．０８ｇを加え、０℃で１２時間攪拌した。反応後、揮発成分を減圧留去し、ヘキサン中にて再結晶を行い、０．１１ｇの無色結晶を得た。１Ｈ－ＮＭＲ、２９Ｓｉ－ＮＭＲおよびＸ線結晶構造解析の結果（図１～３）、得られた結晶は１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンであると同定され、その単離収率は５３％であった。
[Example 1]
Under an inert atmosphere, 0.31 g of diacetoxydi-tert-butoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 ml of hexane were added to the three-necked flask and cooled to 0 ° C. 0.08 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at 0 ° C. for 12 hours. After the reaction, the volatile components were distilled off under reduced pressure and recrystallized in hexane to obtain 0.11 g of colorless crystals. As a result of 1 1 H-NMR, 29 Si-NMR and X-ray crystal structure analysis (Figs. 1 to 3), the obtained crystals were 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane. The isolated yield was 53%.
［実施例２］
不活性雰囲気下にて、三口フラスコにジアセトキシジ－ｔｅｒｔ－ブトキシシラン（信越化学工業株式会社製）０．６１ｇ及びペンタン１６ｍｌを加え、０℃に冷却した。そこへ水酸化ナトリウム０．１７ｇと硫酸ナトリウム０．４６ｇを加え、０℃で１２時間混合攪拌した。反応後、揮発成分を減圧留去し、ヘキサン中にて再結晶を行い、０．２８ｇの無色結晶を得た。１Ｈ－ＮＭＲ、２９Ｓｉ－ＮＭＲおよびＸ線結晶構造解析の結果、得られた結晶は１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンであると同定され、その単離収率は６８％であった。
[Example 2]
Under an inert atmosphere, 0.61 g of diacetoxydi-tert-butoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 16 ml of pentane were added to the three-necked flask, and the mixture was cooled to 0 ° C. To this, 0.17 g of sodium hydroxide and 0.46 g of sodium sulfate were added, and the mixture was mixed and stirred at 0 ° C. for 12 hours. After the reaction, the volatile components were distilled off under reduced pressure and recrystallized in hexane to obtain 0.28 g of colorless crystals. As a result of 1 H-NMR, 29 Si-NMR and X-ray crystal structure analysis, the obtained crystal was identified as 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane. The isolated yield was 68%.
［実施例３］
不活性雰囲気下にて、三口フラスコにジアセトキシジ－ｔｅｒｔ－ブトキシシラン（信越化学工業株式会社製）０．３１ｇ及びペンタン８ｍｌを加え、０℃に冷却した。そこへ水酸化ナトリウム０．０８ｇと硫酸マグネシウム０．１５ｇを加え、０℃で１２時間混合攪拌した。反応後、揮発成分を減圧留去し、ヘキサン中にて再結晶を行い、０．１３ｇの無色結晶を得た。１Ｈ－ＮＭＲ、２９Ｓｉ－ＮＭＲおよびＸ線結晶構造解析の結果、得られた結晶は１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンであると同定され、その単離収率は６８％であった。
[Example 3]
Under an inert atmosphere, 0.31 g of diacetoxydi-tert-butoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 8 ml of pentane were added to the three-necked flask and cooled to 0 ° C. 0.08 g of sodium hydroxide and 0.15 g of magnesium sulfate were added thereto, and the mixture was mixed and stirred at 0 ° C. for 12 hours. After the reaction, the volatile components were distilled off under reduced pressure and recrystallized in hexane to obtain 0.13 g of colorless crystals. As a result of 1 H-NMR, 29 Si-NMR and X-ray crystal structure analysis, the obtained crystal was identified as 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane. The isolated yield was 68%.
［実施例４］
不活性雰囲気下にて、三口フラスコにジアセトキシジ－ｔｅｒｔ－ブトキシシラン（信越化学工業株式会社製）０．３１ｇ及びペンタン８ｍｌを加え、０℃に冷却した。そこへ水酸化カリウム０．１２ｇと硫酸ナトリウム０．２５ｇを加え、０℃で１４時間混合攪拌した。反応後、揮発成分を減圧留去し、ヘキサン中にて再結晶を行うことで、０．０８ｇの無色結晶を得た。１Ｈ－ＮＭＲ、２９Ｓｉ－ＮＭＲおよびＸ線結晶構造解析の結果、得られた結晶は１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンであると同定され、その単離収率は３９％であった。
[Example 4]
Under an inert atmosphere, 0.31 g of diacetoxydi-tert-butoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 8 ml of pentane were added to the three-necked flask and cooled to 0 ° C. To this, 0.12 g of potassium hydroxide and 0.25 g of sodium sulfate were added, and the mixture was mixed and stirred at 0 ° C. for 14 hours. After the reaction, the volatile components were distilled off under reduced pressure and recrystallized in hexane to obtain 0.08 g of colorless crystals. As a result of 1 H-NMR, 29 Si-NMR and X-ray crystal structure analysis, the obtained crystal was identified as 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane. The isolated yield was 39%.
［実施例５］
不活性雰囲気下にて、シュレンク管にジアセトキシジ－ｔｅｒｔ－ブトキシシラン（信越化学工業株式会社製）０．３１ｇ、ヘキサン８ｍｌ、及び内部標準としてメシチレン０．１２ｇを加えた。２５℃にて水酸化ナトリウム０．０８ｇを加え、２５℃で混合攪拌した。水酸化ナトリウムの添加から１時間後、３時間後、７時間後、２２時間後に１Ｈ－ＮＭＲ、２９Ｓｉ－ＮＭＲを測定し、いずれの反応時間においても１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの生成を確認した。
[Example 5]
Under an inert atmosphere, 0.31 g of diacetoxydi-tert-butoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 8 ml of hexane, and 0.12 g of mesitylene as an internal standard were added to the Schlenk tube. 0.08 g of sodium hydroxide was added at 25 ° C., and the mixture was mixed and stirred at 25 ° C. 1 H-NMR and 29 Si-NMR were measured 1 hour, 3 hours, 7 hours, and 22 hours after the addition of sodium hydroxide, and 1,3-dihydroxy-1,1,1 were measured at any reaction time. The formation of 3,3-tetra-tert-butoxydisiloxane was confirmed.
［実施例６］
不活性雰囲気下にて、シュレンク管にジアセトキシジ－ｔｅｒｔ－ブトキシシラン（信越化学工業株式会社製）０．３１ｇ、ヘキサン８ｍｌ、及び内部標準としてメシチレン０．１２ｇを加え、－１０℃に冷却した。水酸化ナトリウム０．０８ｇを加え、－１０℃で混合攪拌した。水酸化ナトリウムの添加から１時間後、３時間後、７時間後、２２時間後に１Ｈ－ＮＭＲ、２９Ｓｉ－ＮＭＲを測定した。反応開始１時間後では１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの生成を確認できなかったが、３時間後、７時間後、２２時間後ではいずれの反応時間においても１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの生成を確認した。
[Example 6]
Under an inert atmosphere, 0.31 g of diacetoxydi-tert-butoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 8 ml of hexane, and 0.12 g of mesitylene as an internal standard were added to the Schlenk tube and cooled to −10 ° C. 0.08 g of sodium hydroxide was added, and the mixture was mixed and stirred at −10 ° C. 1 H-NMR and 29 Si-NMR were measured 1 hour, 3 hours, 7 hours, and 22 hours after the addition of sodium hydroxide. The formation of 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane could not be confirmed 1 hour after the start of the reaction, but any of the following were observed after 3 hours, 7 hours, and 22 hours. The formation of 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane was also confirmed in the reaction time.
［比較例１～４］
下記反応式に示すように、Ｌ、Ｍ（ＯＨ）ｎ及び脱水剤を表１に記載のものを用いて実施例１と同様の手法で反応を行ったが、いずれも反応生成物がゲル状となったため、目的の１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンを得ることができなかった。
As shown in the reaction formula below, the reaction was carried out in the same manner as in Example 1 using L, M (OH) n and the dehydrating agent shown in Table 1, but the reaction products were all in the form of a gel. Therefore, the desired 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane could not be obtained.
実施例１～６の結果より、ジアセトキシジ‐ｔｅｒｔ－ブトキシシランと水酸化ナトリウム又は水酸化カリウムを混合すると、１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンの合成が可能であることが分かる。一方、比較例１～４の結果により、その他の金属の水酸化物を用いたり、ジアセトキシジ‐ｔｅｒｔ－ブトキシシランのアセトキシ基が塩素に置換された化合物を用いたりすると、目的の１，３－ジヒドロキシ－１，１，３，３－テトラ－ｔｅｒｔ－ブトキシジシロキサンを得ることができないことも判明した。 From the results of Examples 1 to 6, when diacetoxydi-tert-butoxysilane and sodium hydroxide or potassium hydroxide are mixed, 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane is synthesized. It turns out that is possible. On the other hand, according to the results of Comparative Examples 1 to 4, when a hydroxide of another metal is used or a compound in which the acetoxy group of diacetoxydi-tert-butoxysilane is replaced with chlorine is used, the target 1,3-dihydroxy is used. It was also found that -1,1,3,3-tetra-tert-butoxydisiloxane could not be obtained.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an example, and the present invention can be anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same function and effect. Is included in the technical scope of.
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