JP2021017427A - Bishaloalkylsiloxane compound and method of producing the same, and method of producing siloxane compound with both terminals functionalized - Google Patents
Bishaloalkylsiloxane compound and method of producing the same, and method of producing siloxane compound with both terminals functionalized Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- -1 siloxane compound Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- LYNCRGYDKRNBAB-UHFFFAOYSA-N 8-chlorooct-1-ene Chemical compound ClCCCCCCC=C LYNCRGYDKRNBAB-UHFFFAOYSA-N 0.000 description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 description 13
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 7
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- PNRGKRPIFIMCGM-UHFFFAOYSA-N CCCCCC(CC([Si](C)(C)O[SiH](C)C)Cl)Cl Chemical compound CCCCCC(CC([Si](C)(C)O[SiH](C)C)Cl)Cl PNRGKRPIFIMCGM-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000010412 perfusion Effects 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BJLJNLUARMMMLW-UHFFFAOYSA-N chloro-(3-chloropropyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCCCl BJLJNLUARMMMLW-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、ビスハロアルキルシロキサン化合物及びその製造方法に関する。本発明はまた、ビスハロアルキルシロキサン化合物を用いて両末端官能性のシロキサン化合物を製造する方法に関する。 The present invention relates to a bishaloalkylsiloxane compound and a method for producing the same. The present invention also relates to a method for producing a bilaterally functional siloxane compound using a bishaloalkylsiloxane compound.
ケイ素原子に結合したハロアルキル基を有する有機ケイ素化合物は、有機反応によってハロゲノ基を各種の官能基を有する置換基で置換することにより、種々の官能性有機ケイ素化合物を得るための中間体として有用である。例えば、非特許文献１は、アリルクロリドとジメチル水素クロロシランとのヒドロシリル化反応により生成したクロロプロピルジメチルクロロシラン（ＣｌＭｅ２ＳｉＣＨ２ＣＨ２ＣＨ２Ｃｌ）を単離し、これを加水分解する方法により、クロロプロピル基を有するジシロキサン化合物を製造したことを報告している。 Organosilicon compounds having a haloalkyl group bonded to a silicon atom are useful as intermediates for obtaining various functional organosilicon compounds by substituting a halogeno group with a substituent having various functional groups by an organic reaction. is there. For example, Non-Patent Document 1 describes chloro by a method of isolating chloropropyldimethylchlorosilane (ClMe 2 SiCH 2 CH 2 CH 2 Cl) produced by a hydrosilylation reaction of allyl chloride and dimethylhydrochlorosilane and hydrolyzing it. It has been reported that a disiloxane compound having a propyl group was produced.
本発明の一側面は、両末端官能性のシロキサン化合物を合成するための中間体等として有用な、新規なビスアルキルシロキサン化合物、及びその製造方法を提供する。 One aspect of the present invention provides a novel bisalkylsiloxane compound, which is useful as an intermediate for synthesizing a siloxane compound having both terminal functionality, and a method for producing the same.
本発明の一側面は、下記式（１）で表される、ビスハロアルキルシロキサン化合物に関する。 One aspect of the present invention relates to a bishaloalkylsiloxane compound represented by the following formula (1).
式（１）中、Ｘはハロゲン原子を示し、Ｒ１は炭素数３〜７のアルキレン基を示し、Ｒ２は炭素数１〜３のアルキル基、又はフェニル基を示し、同一分子中の複数のＲ２は同一でも異なっていてもよく、ｎは０〜２００の整数を示す。 In the formula (1), X represents a halogen atom, R 1 represents an alkylene group having 3 to 7 carbon atoms, R 2 represents an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and a plurality of groups in the same molecule. R 2 may be the same or different, and n represents an integer from 0 to 200.
本発明の別の一側面は、上記ビスハロアルキルシロキサン化合物を製造する方法に関する。本発明の一側面に係る方法は、下記式（２）で表されるハロオレフィン化合物と下記式（３）で表されるシロキサン化合物とのヒドロシリル化反応によって、式（１）で表されるビスハロアルキルシロキサン化合物を生成させる工程を含む。 Another aspect of the present invention relates to a method for producing the bishaloalkylsiloxane compound. The method according to one aspect of the present invention is a bis represented by the formula (1) by a hydrosilylation reaction between a haloolefin compound represented by the following formula (2) and a siloxane compound represented by the following formula (3). The step of producing a haloalkylsiloxane compound is included.
本発明の更に別の一側面は、上記ビスアルキルシロキサン化合物のハロゲン原子を、官能基を含む置換基に置換する工程を含む、両末端官能性のシロキサン化合物を製造する方法に関する。 Yet another aspect of the present invention relates to a method for producing a siloxane compound having both terminal functionality, which comprises a step of substituting a halogen atom of the bisalkylsiloxane compound with a substituent containing a functional group.
本発明の一側面に係るビスハロアルキルシロキサン化合物は、両末端官能性のシロキサン化合物を合成するための中間体等として有用である。本発明の一側面に係る製造方法によれば、ビスハロアルキルシロキサン化合物を、比較的温和な反応条件で、副生物が少なく高い収率で得ることができる。 The bishaloalkylsiloxane compound according to one aspect of the present invention is useful as an intermediate or the like for synthesizing a siloxane compound having both terminal functionality. According to the production method according to one aspect of the present invention, the bishaloalkylsiloxane compound can be obtained in a high yield with few by-products under relatively mild reaction conditions.
以下、本発明のいくつかの実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
ビスハロアルキルシロキサン化合物を製造する方法の一実施形態は、下記式（２）で表されるハロオレフィン化合物と下記式（３）で表されるシロキサン化合物とのヒドロシリル化反応によって、下記式（１）で表されるビスハロアルキルシロキサン化合物を生成させる工程を含む。 One embodiment of the method for producing a bishaloalkylsiloxane compound is a hydrosilylation reaction between a haloolefin compound represented by the following formula (2) and a siloxane compound represented by the following formula (3) to carry out the following formula (1). Including a step of producing a bishaloalkylsiloxane compound represented by.
式（１）、（２）及び（３）中、Ｘはハロゲン原子を示し、Ｒ１は炭素数３〜７のアルキレン基を示し、Ｒ２は炭素数１〜３のアルキル基、又はフェニル基を示し、同一分子中の複数のＲ２は同一でも異なっていてもよい。ｎは０〜２００の整数を示す。 In formulas (1), (2) and (3), X represents a halogen atom, R 1 represents an alkylene group having 3 to 7 carbon atoms, and R 2 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. are shown, multiple R 2 in the same molecule may be the same or different. n represents an integer from 0 to 200.
式（２）で表されるハロオレフィン化合物を用いたヒドロシリル化反応により、ビスハロアルキルシロキサン化合物を、副生物が少なく高い収率で生成させることができる。非特許文献１が報告したような、アリルクロリドのヒドロシリル化反応の場合、β−付加によって生成した化合物からクロロシランが脱離する副反応が生じ易い。更に、クロロシランはクロロシロキサンを副生物として生成させる。したがって、目的とするクロロプロピルジメチルクロロシランの収率は極めて低く、この反応は実用に耐えるものではなかった。これに対して、式（２）のハロオレフィン化合物の場合、末端のビニル基とハロゲン原子が結合した炭素原子との間に、炭素数３以上のアルキレン基Ｒ１が存在するため、β−付加の生成物からクロロシランが脱離することがなく、このことが収率向上に寄与すると考えられる。また、式（２）のハロオレフィン化合物は比較的高い沸点を有するため、高圧条件を必要とすることなく、常圧でヒドロシリル化反応が進行する温度まで加熱することができる。加えて、加水分解の工程を経ることなく、ヒドロシリル化反応だけでビスハロアルキルシロキサン化合物が生成する点でも、本実施形態に係る方法は優れている。 A bishaloalkylsiloxane compound can be produced in a high yield with few by-products by a hydrosilylation reaction using a haloolefin compound represented by the formula (2). In the case of the hydrosilylation reaction of allyl chloride as reported in Non-Patent Document 1, a side reaction in which chlorosilane is eliminated from the compound produced by β-addition is likely to occur. In addition, chlorosilane produces chlorosiloxane as a by-product. Therefore, the yield of the desired chloropropyldimethylchlorosilane was extremely low, and this reaction was not practical. In contrast, in the case of halo-olefin compound of formula (2), between the carbon atom to which the vinyl group and a halogen atom of the terminal is bonded, because of the presence of an alkylene group R 1 having 3 or more carbon atoms, beta-it added Chlorosilane is not desorbed from the product of, which is considered to contribute to the improvement of yield. Further, since the haloolefin compound of the formula (2) has a relatively high boiling point, it can be heated to a temperature at which the hydrosilylation reaction proceeds at normal pressure without requiring high pressure conditions. In addition, the method according to the present embodiment is excellent in that a bishaloalkylsiloxane compound is produced only by a hydrosilylation reaction without going through a hydrolysis step.
式（１）中のＸは、塩素原子又は臭素原子であってもよく、特に塩素原子であってもよい。Ｒ１は直鎖状、分岐状、環状、又はこれらの組み合わせを含むアルキレン基であってもよく、直鎖アルキレン基であってもよい。Ｒ１が炭素数５の直鎖アルキレン基であってもよい。式（１）のハロオレフィン化合物の具体例としては、１−クロロオクト−７−エンが挙げられる。 X in the formula (1) may be a chlorine atom or a bromine atom, and may be a chlorine atom in particular. R 1 may be an alkylene group containing a linear, branched, cyclic, or a combination thereof, or may be a linear alkylene group. R 1 may be a linear alkylene group having 5 carbon atoms. Specific examples of the haloolefin compound of the formula (1) include 1-chlorooct-7-ene.
式（２）中のＲ２は、メチル基、エチル基、又はｎ−プロピル基であってもよく、メチル基であってもよい。ｎは０〜２００の整数であり、０〜１５０又は０〜１００の整数であってもよい。 R 2 in the formula (2) may be a methyl group, an ethyl group, an n-propyl group, or a methyl group. n is an integer from 0 to 200 and may be an integer from 0 to 150 or 0 to 100.
ヒドロシリル化反応は、触媒の存在下で行ってもよい。触媒はヒドロシリル化反応の触媒として通常用いられるものから選択できる。触媒の例としては、塩化白金酸、及びジビニルテトラメチルジシロキサンの白金錯体のような白金触媒が挙げられる。白金触媒は、イソプロパノール等の溶媒を含む溶液の状態で、反応液に添加されてもよい。 The hydrosilylation reaction may be carried out in the presence of a catalyst. The catalyst can be selected from those commonly used as catalysts for the hydrosilylation reaction. Examples of catalysts include platinum catalysts such as chloroplatinic acid and a platinum complex of divinyltetramethyldisiloxane. The platinum catalyst may be added to the reaction solution in the form of a solution containing a solvent such as isopropanol.
ヒドロシリル化反応は、無溶媒の反応液、又は溶媒を含む反応液中で行うことができる。反応温度（反応液の温度）及び反応時間は、ヒドロシリル化反応が充分に進行するように、調整される。例えば、反応温度は５０℃〜１８０℃、又は８０℃〜１３０℃であってもよい。反応時間は１〜３時間であってもよい。 The hydrosilylation reaction can be carried out in a solvent-free reaction solution or a reaction solution containing a solvent. The reaction temperature (temperature of the reaction solution) and the reaction time are adjusted so that the hydrosilylation reaction proceeds sufficiently. For example, the reaction temperature may be 50 ° C. to 180 ° C. or 80 ° C. to 130 ° C. The reaction time may be 1-3 hours.
ヒドロシリル化反応によって得られた式（１）のビスハロアルキルシロキサン化合物を、環状シロキサンオリゴマー（例えばオクタメチルシクロテトラシロキサン）と反応させることより、更に長いポリシロキサン鎖を有するビスハロアルキルシロキサン化合物を得ることもできる。 By reacting the bishaloalkylsiloxane compound of the formula (1) obtained by the hydrosilylation reaction with a cyclic siloxane oligomer (for example, octamethylcyclotetrasiloxane), a bishaloalkylsiloxane compound having a longer polysiloxane chain can be obtained. it can.
式（１）のビスハロアルキルシロキサン化合物を、両末端官能性の各種シロキサン化合物を製造するために用いてもよい。例えば、ビスアルキルシロキサン化合物のハロゲン原子を、官能基を含む置換基に置換する工程を含む方法により、両末端官能性のシロキサン化合物を製造することができる。 The bishaloalkylsiloxane compound of the formula (1) may be used to produce various siloxane compounds having both terminal functionality. For example, a siloxane compound having both terminal functionality can be produced by a method including a step of substituting a halogen atom of a bisalkylsiloxane compound with a substituent containing a functional group.
導入される官能基の例としては、アミノ基、アセトキシ基、（メタ）アクリロイルオキシ基が挙げられる。 Examples of functional groups to be introduced include amino groups, acetoxy groups and (meth) acryloyloxy groups.
導入される官能基自体がハロアルキル基と反応する場合、導入される官能基を有する化合物と式（２）のビスハロアルキルシロキサン化合物との反応によって、両末端官能性のシロキサン化合物を得ることができる。例えば、有機アミン化合物を用いることにより、アミノ基を導入することができる。あるいは、酢酸又は（メタ）アクリル酸のアルカリ金属塩を用いることにより、アセトキシ基又は（メタ）アクリロイルオキシ基を導入してもよい。導入される官能基とハロアルキル基と反応する反応基とを有する化合物を、式（２）のビスハロアルキルシロキサン化合物と反応させてもよい。反応条件は、当業者に理解されるように、通常の置換反応の範囲で、適宜調整される。 When the functional group to be introduced reacts with a haloalkyl group, a siloxane compound having both terminal functionality can be obtained by reacting the compound having the functional group to be introduced with the bishaloalkylsiloxane compound of the formula (2). For example, an amino group can be introduced by using an organic amine compound. Alternatively, an acetoxy group or a (meth) acryloyloxy group may be introduced by using an alkali metal salt of acetic acid or (meth) acrylic acid. A compound having a functional group to be introduced and a reactive group that reacts with a haloalkyl group may be reacted with a bishaloalkylsiloxane compound of the formula (2). The reaction conditions are appropriately adjusted within the range of the usual substitution reaction, as will be understood by those skilled in the art.
合成される両末端官能性のシロキサン化合物は、例えば下記式（５）で表される化合物であることができる。
式（５）中のＺは、官能基を含む置換基である。Ｚは、例えば、アルキルアミノ基、アセトキシ基、又は（メタ）アクリロイルオキシ基であることができる。Ｒ１、Ｒ２及びｎは式（１）〜（３）中のＲ１、Ｒ２及びｎと同義である。
The both-terminal functional siloxane compound to be synthesized can be, for example, a compound represented by the following formula (5).
Z in the formula (5) is a substituent containing a functional group. Z can be, for example, an alkylamino group, an acetoxy group, or a (meth) acryloyloxy group. R 1, R 2 and n have the same meanings as R 1, R 2 and n in formula (1) to (3).
両末端官能性のシロキサン化合物は、例えば、ＵＶコーティング剤等の塗料の成分として適用可能である。 The bi-terminal functional siloxane compound can be applied as a component of a coating material such as a UV coating agent.
以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
１，３−ビスクロロオクチル−１，１，３，３−テトラメチルジシロキサン（式（１）において、Ｘが塩素原子、Ｒ１が炭素数５のアルキレン基、Ｒ２がメチル基、ｎが０である化合物）の合成
還流管、滴下ロート、温度計を備えた５００ミリリットルの三口丸底フラスコに、１−クロロオクト−７−エンを２３５ｇ、ジビニルテトラメチルジシロキサン白金錯体のジビニルテトラメチルジシロキサン溶液（白金含有量：２％）を６０ｍｇ入れた。フラスコ内の反応液を磁気攪拌子で撹拌しながら１１０℃まで加熱した。加熱を止め、１，１，３，３−テトラメチルジシロキサン６７．２ｇを、１１０℃から１２０℃を維持しながら反応液にゆっくりと滴下した。滴下終了後、反応液の温度を１２０℃で１時間維持した。未反応の１−クロロオクト−７−エンを減圧下で留去し、次いで１，３−ビスクロロオクチル−１，１，３，３−テトラメチルジシロキサンを減圧蒸留で単離した。単離した生成物の沸点は０．０７ｋＰａの圧力下で１７８℃〜１７９℃であった。収量は１９７ｇで、収率は滴下した１，１，３，３−テトラメチルジシロキサンに対して９２％であった。生成物のガスクロマトグラフィーによる純度は９９％であった。図１は、単離された生成物のＦＴ−ＩＲスペクトルである。図２及び図３は、それぞれ、原料として用いられた１，１，３，３−テトラメチルジシロキサン及び１−クロロオクト−７−エンのＦＴ−ＩＲスペクトルである。１，１，３，３−テトラメチルジシロキサンで観測された２１００ｃｍ−１付近のＳｉ−Ｈの吸収、及び１−クロロオクト−７−エンで観測された１６４０ｃｍ−１付近のオレフィンの吸収が、生成物のＦＴ−ＩＲスペクトルにおいて消失しており、このことから目的とする１，３−ビスクロロオクチル−１，１，３，３−テトラメチルジシロキサンが生成していることが確認された。生成物の構造は、図４の１Ｈ ＮＭＲスペクトル（ＣＤＣｌ３，内部標準物質：テトラメチルシラン）、及び以下の元素分析の結果からも確認された。
元素分析値：Ｃ ５６．２％（理論値：５６．１７％）；Ｈ １０．４％（理論値：１０．３７％）
(Example 1)
1,3-bischlorooctyl-1,1,3,3-tetramethyldisiloxane (in formula (1), X is a chlorine atom, R 1 is an alkylene group having 5 carbon atoms, R 2 is a methyl group, and n is. Synthesis of compound (0) In a 500 ml three-necked round bottom flask equipped with a perfusion tube, a dropping funnel, and a thermometer, 235 g of 1-chlorooct-7-ene and divinyltetramethyldisiloxane of a divinyltetramethyldisiloxane platinum complex 60 mg of the solution (platinum content: 2%) was added. The reaction solution in the flask was heated to 110 ° C. while stirring with a magnetic stir bar. The heating was stopped, and 67.2 g of 1,1,3,3-tetramethyldisiloxane was slowly added dropwise to the reaction solution while maintaining 110 ° C to 120 ° C. After completion of the dropping, the temperature of the reaction solution was maintained at 120 ° C. for 1 hour. Unreacted 1-chlorooct-7-ene was distilled off under reduced pressure, and then 1,3-bischlorooctyl-1,1,3,3-tetramethyldisiloxane was isolated by vacuum distillation. The boiling point of the isolated product was 178 ° C to 179 ° C under a pressure of 0.07 kPa. The yield was 197 g, and the yield was 92% with respect to the dropped 1,1,3,3-tetramethyldisiloxane. The purity of the product by gas chromatography was 99%. FIG. 1 is an FT-IR spectrum of the isolated product. 2 and 3 are FT-IR spectra of 1,1,3,3-tetramethyldisiloxane and 1-chlorooct-7-ene used as raw materials, respectively. Absorption of Si-H near 2100 cm- 1 observed with 1,1,3,3-tetramethyldisiloxane and absorption of olefins near 1640 cm- 1 observed with 1-chlorooct-7-ene are produced. It disappeared in the FT-IR spectrum of the product, and it was confirmed from this that the desired 1,3-bischlorooctyl-1,1,3,3-tetramethyldisiloxane was produced. The structure of the product was also confirmed from the 1 H NMR spectrum of FIG. 4 (CDCl 3 , internal standard substance: tetramethylsilane) and the results of the following elemental analysis.
Elemental analysis value: C 56.2% (theoretical value: 56.17%); H 10.4% (theoretical value: 10.37%)
（実施例２）
両末端にクロロオクチル基を有するジメチルポリシロキサン（式（１）において、Ｘが塩素原子、Ｒ１が炭素数５のアルキレン基、Ｒ２がメチル基、ｎが平均で１５である化合物）の合成
還流管、滴下ロート、撹拌棒、温度計を備えた２リットルの四口丸底フラスコに、両末端にジメチルヒドロシリル基を有するポリジメチルシロキサン（平均組成式：ＨＭｅ２ＳｉＯ（Ｍｅ２ＳｉＯ）１５ＳｉＭｅ２Ｈ）を１３７０ｇ、ジビニルテトラメチルジシロキサン白金錯体のジビニルテトラメチルジシロキサン溶液（白金含有量：２％）を１００ｍｇ入れた。フラスコ内の反応液を磁気攪拌子で攪拌しながら１１０℃まで加熱した。続いて反応液に対して１−クロロオクト−７−エン４４０ｇをゆっくりと滴下した。滴下終了後、１１０℃〜１２５℃の温度を維持しながら、反応液を１時間撹拌した。０．２ｋＰａの減圧下、フラスコ内の温度１４５℃の条件で未反応の１−クロロオクト−７−エン、及び並行反応によって生成した環状ポリジメチルシロキサンを留去した。残渣のろ過により、１１１０ｇの生成物を得た。図５は、単離された生成物のＦＴ−ＩＲスペクトルである。１，１，３，３−テトラメチルジシロキサンで観測された２１００ｃｍ−１付近のＳｉ−Ｈの吸収、及び１−クロロオクト−７−エンで観測された１６４０ｃｍ−１付近のオレフィンの吸収が、生成物のＦＴ−ＩＲスペクトルにおいて消失しており、このことから目的物である両末端にクロロオクチル基を有するジメチルポリシロキサンが得られたことを確認した。
(Example 2)
Synthesis of dimethylpolysiloxane having chlorooctyl groups at both ends (in formula (1), X is a chlorine atom, R 1 is an alkylene group having 5 carbon atoms, R 2 is a methyl group, and n is an average of 15 compounds). Polydimethylsiloxane having dimethylhydrosilyl groups at both ends in a 2-liter four-necked round-bottomed flask equipped with a perfusion tube, dropping funnel, stirring rod, and thermometer (average composition formula: HMe 2 SiO (Me 2 SiO) 15 SiMe 2 H) and 1370 g, divinyltetramethyldisiloxane platinum complex of divinyltetramethyldisiloxane solution (platinum content: 2%) were placed 100 mg. The reaction solution in the flask was heated to 110 ° C. while stirring with a magnetic stir bar. Subsequently, 440 g of 1-chlorooct-7-ene was slowly added dropwise to the reaction solution. After completion of the dropping, the reaction solution was stirred for 1 hour while maintaining the temperature of 110 ° C. to 125 ° C. Under a reduced pressure of 0.2 kPa, unreacted 1-chlorooct-7-ene and cyclic polydimethylsiloxane produced by the parallel reaction were distilled off under the condition of a temperature of 145 ° C. in the flask. Filtration of the residue gave 1110 g of product. FIG. 5 is an FT-IR spectrum of the isolated product. Absorption of Si-H near 2100 cm- 1 observed with 1,1,3,3-tetramethyldisiloxane and absorption of olefins near 1640 cm- 1 observed with 1-chlorooct-7-ene are produced. It disappeared in the FT-IR spectrum of the product, and from this, it was confirmed that the desired dimethylpolysiloxane having chlorooctyl groups at both ends was obtained.
（実施例３）
両末端にクロロオクチル基を有するジメチルポリシロキサン（式（１）において、Ｘが塩素原子、Ｒ１が炭素数５のアルキレン基、Ｒ２がメチル基、ｎが平均で６５である化合物）の合成
還流管、滴下ロート、撹拌棒、温度計を備えた５００ミリリットルの四口丸底フラスコに、両末端にジメチルヒドロシリル基を有するポリジメチルシロキサン（平均組成式：ＨＭｅ２ＳｉＯ（Ｍｅ２ＳｉＯ）６５ＳｉＭｅ２Ｈ）を３００ｇ、ジビニルテトラメチルジシロキサン白金錯体のジビニルテトラメチルジシロキサン溶液（白金含有量：２％）を１−クロロオクト−７−エンに対して１０ｐｐｍに相当する量を入れた。フラスコ内の反応液を磁気攪拌子で攪拌しながら１１０℃まで加熱した。続いて反応液に対して１−クロロオクト−７−エン３３．３ｇをゆっくりと滴下した。滴下終了後、１１０℃〜１２５℃の温度を維持しながら、反応液を１時間撹拌した。０．２ｋＰａの減圧下、フラスコ内の温度１４５℃の条件で未反応の１−クロロオクト−７−エン、及び並行反応によって生成した環状ポリジメチルシロキサンを留去した。残渣のろ過により、２９０．３ｇの生成物を得た。生成物のＦＴ−ＩＲによる実施例１、２と同様の分析から、目的物である両末端にクロロオクチル基を有するジメチルポリシロキサンが得られたことを確認した。
(Example 3)
Synthesis of dimethylpolysiloxane having chlorooctyl groups at both ends (in formula (1), X is a chlorine atom, R 1 is an alkylene group having 5 carbon atoms, R 2 is a methyl group, and n is an average of 65). Polydimethylsiloxane having dimethylhydrosilyl groups at both ends in a 500 ml four-necked round bottom flask equipped with a perfusion tube, a dropping funnel, a stirring rod, and a thermometer (average composition formula: HMe 2 SiO (Me 2 SiO) 65 SiMe 2 H) and 300 g, divinyltetramethyldisiloxane siloxane platinum complex divinyltetramethyldisiloxane solution (platinum content: put an amount corresponding to 10ppm with respect to 2%) of 1-Kurorookuto-7-ene. The reaction solution in the flask was heated to 110 ° C. while stirring with a magnetic stir bar. Subsequently, 33.3 g of 1-chlorooct-7-ene was slowly added dropwise to the reaction solution. After completion of the dropping, the reaction solution was stirred for 1 hour while maintaining the temperature of 110 ° C. to 125 ° C. Under a reduced pressure of 0.2 kPa, unreacted 1-chlorooct-7-ene and cyclic polydimethylsiloxane produced by the parallel reaction were distilled off under the condition of a temperature of 145 ° C. in the flask. Filtration of the residue gave 290.3 g of product. From the same analysis as in Examples 1 and 2 by FT-IR of the product, it was confirmed that the desired dimethylpolysiloxane having chlorooctyl groups at both ends was obtained.
（実施例４）
両末端にクロロオクチル基を有するジメチルポリシロキサン（式（１）において、Ｘが塩素原子、Ｒ１が炭素数５のアルキレン基、Ｒ２がメチル基、ｎが平均で１００である化合物）の合成
還流管、滴下ロート、撹拌棒、温度計を備えた５００ミリリットルの四口丸底フラスコに、両末端にジメチルヒドロシリル基を有するポリジメチルシロキサン（平均組成式：ＨＭｅ２ＳｉＯ（Ｍｅ２ＳｉＯ）１００ＳｉＭｅ２Ｈ）を３００ｇ、ジビニルテトラメチルジシロキサン白金錯体のジビニルテトラメチルジシロキサン溶液（白金含有量：２％）を１−クロロオクト−７−エンに対して１０ｐｐｍに相当する量を入れた。フラスコ内の反応液を磁気攪拌子で攪拌しながら１１０℃まで加熱した。続いて反応液に対して１−クロロオクト−７−エン２１．９ｇをゆっくりと滴下した。滴下終了後、１１０℃〜１２５℃の温度を維持しながら、反応液を１時間撹拌した。１ｍｍＨｇの減圧下、フラスコ内の温度１５０℃の条件で未反応の１−クロロオクト−７−エン、及び並行反応によって生成した環状ポリジメチルシロキサンを留去した。残渣のろ過により、２６６．３ｇの生成物を得た。生成物のＦＴ−ＩＲによる実施例１、２と同様の分析から、目的物である両末端にクロロオクチル基を有するジメチルポリシロキサンが得られたことを確認した。
(Example 4)
Synthesis of dimethylpolysiloxane having chlorooctyl groups at both ends (in formula (1), X is a chlorine atom, R 1 is an alkylene group having 5 carbon atoms, R 2 is a methyl group, and n is an average of 100). Polydimethylsiloxane having dimethylhydrosilyl groups at both ends in a 500 ml four-necked round bottom flask equipped with a reflux tube, a dropping funnel, a stirring rod, and a thermometer (average composition formula: HMe 2 SiO (Me 2 SiO) 100 SiMe 2 H) and 300 g, divinyltetramethyldisiloxane siloxane platinum complex divinyltetramethyldisiloxane solution (platinum content: put an amount corresponding to 10ppm with respect to 2%) of 1-Kurorookuto-7-ene. The reaction solution in the flask was heated to 110 ° C. while stirring with a magnetic stir bar. Subsequently, 21.9 g of 1-chlorooct-7-ene was slowly added dropwise to the reaction solution. After completion of the dropping, the reaction solution was stirred for 1 hour while maintaining the temperature of 110 ° C. to 125 ° C. Under a reduced pressure of 1 mmHg, unreacted 1-chlorooct-7-ene and cyclic polydimethylsiloxane produced by the parallel reaction were distilled off under the condition of a temperature of 150 ° C. in the flask. Filtration of the residue gave 266.3 g of product. From the same analysis as in Examples 1 and 2 by FT-IR of the product, it was confirmed that the desired dimethylpolysiloxane having chlorooctyl groups at both ends was obtained.
Claims (3)
［式中、Ｘはハロゲン原子を示し、Ｒ１は炭素数３〜７のアルキレン基を示し、Ｒ２は炭素数１〜３のアルキル基、又はフェニル基を示し、同一分子中の複数のＲ２は同一でも異なっていてもよく、ｎは０〜２００の整数を示す。］ A bishaloalkylsiloxane compound represented by the following formula (1).
[In the formula, X represents a halogen atom, R 1 represents an alkylene group having 3 to 7 carbon atoms, R 2 represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, and a plurality of Rs in the same molecule. 2 may be the same or different, and n represents an integer from 0 to 200. ]
［式中、Ｘはハロゲン原子を示し、Ｒ１は炭素数３〜７のアルキレン基を示し、Ｒ２は炭素数１〜３のアルキル基、又はフェニル基を示し、同一分子中の複数のＲ２は同一でも異なっていてもよく、ｎは０〜２００の整数を示す。］ It includes a step of producing a bishaloalkylsiloxane compound represented by the following formula (1) by a hydrosilylation reaction between a haloolefin compound represented by the following formula (2) and a siloxane compound represented by the following formula (3). , A method for producing a bishaloalkylsiloxane compound.
[In the formula, X represents a halogen atom, R 1 represents an alkylene group having 3 to 7 carbon atoms, R 2 represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, and a plurality of Rs in the same molecule. 2 may be the same or different, and n represents an integer from 0 to 200. ]
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2770633A (en) * | 1953-10-28 | 1956-11-13 | Dow Corning | Organosilicon esters |
| JPH0368589A (en) * | 1989-07-19 | 1991-03-25 | Dow Corning Corp | Preparation of silyl functional fumarate |
| JPH05117128A (en) * | 1982-11-10 | 1993-05-14 | L'oreal Sa | Cosmetic composition |
| JPH06287305A (en) * | 1993-03-31 | 1994-10-11 | Shin Etsu Chem Co Ltd | Preparation of (meth) acrylic-functional organosilicon compound |
| JP2003048985A (en) * | 2001-07-06 | 2003-02-21 | Degussa Ag | Siloxane oligomer, method for producing the same, use of the same and rubber mixture containing the same by itself |
| JP2009179596A (en) * | 2008-01-30 | 2009-08-13 | Kuraray Medical Inc | Polymerizable monomer suitable for dental material |
| US20100004202A1 (en) * | 2008-02-15 | 2010-01-07 | Ndsu Research Foundation | Quaternary ammonium-functionalized-POSS compounds |
| KR20120007172A (en) * | 2010-07-14 | 2012-01-20 | 주식회사 에이씨엠 | New imidazolium salts and electrolyte composition for dye-sensitized sollar cells containing the salt |
| WO2012010918A2 (en) * | 2010-07-21 | 2012-01-26 | Medicontur Orvostechnikai Kft. | Optical devices |
| JP2013527286A (en) * | 2010-05-19 | 2013-06-27 | エヴォニク ゴールドシュミット ゲーエムベーハー | Polysiloxane block copolymers and their use in cosmetic formulations |
| JP2018193492A (en) * | 2017-05-18 | 2018-12-06 | 信越化学工業株式会社 | Method for producing polymerizable group-containing organopolysiloxane |
-
2019
- 2019-07-23 JP JP2019135388A patent/JP7350253B2/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2770633A (en) * | 1953-10-28 | 1956-11-13 | Dow Corning | Organosilicon esters |
| JPH05117128A (en) * | 1982-11-10 | 1993-05-14 | L'oreal Sa | Cosmetic composition |
| JPH0368589A (en) * | 1989-07-19 | 1991-03-25 | Dow Corning Corp | Preparation of silyl functional fumarate |
| JPH06287305A (en) * | 1993-03-31 | 1994-10-11 | Shin Etsu Chem Co Ltd | Preparation of (meth) acrylic-functional organosilicon compound |
| JP2003048985A (en) * | 2001-07-06 | 2003-02-21 | Degussa Ag | Siloxane oligomer, method for producing the same, use of the same and rubber mixture containing the same by itself |
| JP2009179596A (en) * | 2008-01-30 | 2009-08-13 | Kuraray Medical Inc | Polymerizable monomer suitable for dental material |
| US20100004202A1 (en) * | 2008-02-15 | 2010-01-07 | Ndsu Research Foundation | Quaternary ammonium-functionalized-POSS compounds |
| JP2013527286A (en) * | 2010-05-19 | 2013-06-27 | エヴォニク ゴールドシュミット ゲーエムベーハー | Polysiloxane block copolymers and their use in cosmetic formulations |
| KR20120007172A (en) * | 2010-07-14 | 2012-01-20 | 주식회사 에이씨엠 | New imidazolium salts and electrolyte composition for dye-sensitized sollar cells containing the salt |
| WO2012010918A2 (en) * | 2010-07-21 | 2012-01-26 | Medicontur Orvostechnikai Kft. | Optical devices |
| JP2018193492A (en) * | 2017-05-18 | 2018-12-06 | 信越化学工業株式会社 | Method for producing polymerizable group-containing organopolysiloxane |
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