JP7350253B2 - Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities - Google Patents
Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities Download PDFInfo
- Publication number
- JP7350253B2 JP7350253B2 JP2019135388A JP2019135388A JP7350253B2 JP 7350253 B2 JP7350253 B2 JP 7350253B2 JP 2019135388 A JP2019135388 A JP 2019135388A JP 2019135388 A JP2019135388 A JP 2019135388A JP 7350253 B2 JP7350253 B2 JP 7350253B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- producing
- bishaloalkylsiloxane
- formula
- 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.)
- Active
Links
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 bi-terminally 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 through an organic reaction. be. For example, Non-Patent Document 1 discloses that chloropropyldimethylchlorosilane (ClMe 2 SiCH 2 CH 2 CH 2 Cl) produced by a hydrosilylation reaction of allyl chloride and dimethylhydrogen chlorosilane is isolated and hydrolyzed to produce chlorosilane. 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 that is useful as an intermediate for synthesizing a siloxane compound having 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 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 multiple R 2 may be the same or different, and n represents an integer of 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 of manufacturing the above bishaloalkylsiloxane compound. In the method according to one aspect of the present invention, a haloolefin compound represented by the following formula (2) and a siloxane compound represented by the following formula (3) are subjected to a hydrosilylation reaction to form a bisylamine compound represented by the formula (1). The method includes a step of producing a haloalkylsiloxane compound.
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 functional groups at both ends, which includes 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 for synthesizing a siloxane compound having functional properties at both ends. According to the production method according to one aspect of the present invention, a bishaloalkylsiloxane compound can be obtained under relatively mild reaction conditions with a high yield and few by-products.
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, several 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 to produce the 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). The method includes 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. , and 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。 By the hydrosilylation reaction using the haloolefin compound represented by formula (2), a bishaloalkylsiloxane compound can be produced in high yield with few by-products. 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 tends to occur. Furthermore, chlorosilane produces chlorosiloxane as a by-product. Therefore, the yield of the desired chloropropyldimethylchlorosilane was extremely low, and this reaction was not practical. On the other hand, in the case of the haloolefin compound of formula (2), an alkylene group R 1 having 3 or more carbon atoms exists between the terminal vinyl group and the carbon atom to which the halogen atom is bonded, so β-addition The chlorosilane is not desorbed from the product, which is thought to contribute to the improvement in yield. Further, since the haloolefin compound of 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 also 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 formula (1) may be a chlorine atom or a bromine atom, particularly a chlorine atom. R 1 may be a linear, branched, cyclic, or a combination thereof, or may be a linear alkylene group. R 1 may be a straight chain alkylene group having 5 carbon atoms. A specific example of the haloolefin compound of formula (1) is 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 formula (2) may be a methyl group, an ethyl group, or an n-propyl group, or may be a methyl group. n is an integer of 0 to 200, and may be an integer of 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 hydrosilylation reactions. Examples of catalysts include platinum catalysts such as chloroplatinic acid and platinum complexes 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 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 to 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。 A bishaloalkylsiloxane compound having an even longer polysiloxane chain can also be obtained by reacting the bishaloalkylsiloxane compound of formula (1) obtained by the hydrosilylation reaction with a cyclic siloxane oligomer (e.g., octamethylcyclotetrasiloxane). 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 formula (1) may be used to produce various terminally functional siloxane compounds. For example, a siloxane compound having functionality at both ends 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 the functional groups to be introduced include an amino group, an acetoxy group, and a (meth)acryloyloxy group.
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 introduced functional group itself reacts with a haloalkyl group, a siloxane compound having both terminal functionalities can be obtained by reacting a compound having the introduced functional group with the bishaloalkylsiloxane compound of 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 the bishaloalkylsiloxane compound of formula (2). The reaction conditions are appropriately adjusted within the range of ordinary substitution reactions, as 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 siloxane compound having functionalities at both ends to be synthesized can be, for example, a compound represented by the following formula (5).
Z in 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 formulas (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。 Siloxane compounds having both terminal functionalities can be applied, for example, as a component of paints such as UV coating agents.
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 explained 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 reflux tube, dropping funnel, and thermometer, 235 g of 1-chlorooct-7-ene and divinyltetramethyldisiloxane, a platinum complex of divinyltetramethyldisiloxane. 60 mg of solution (platinum content: 2%) was added. The reaction solution in the flask was heated to 110° C. while stirring with a magnetic stirrer. Heating was stopped, and 67.2 g of 1,1,3,3-tetramethyldisiloxane was slowly added dropwise to the reaction solution while maintaining the temperature from 110°C to 120°C. After the dropwise addition was completed, 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.-179° C. under a pressure of 0.07 kPa. The yield was 197 g, which was 92% based on the 1,1,3,3-tetramethyldisiloxane added dropwise. The purity of the product by gas chromatography was 99%. Figure 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, respectively, used as raw materials. The Si-H absorption near 2100 cm -1 observed for 1,1,3,3-tetramethyldisiloxane and the olefin absorption near 1640 cm -1 observed for 1-chlorooct-7-ene are due to the formation It disappeared in the FT-IR spectrum of the product, which confirmed that the target 1,3-bischlorooctyl-1,1,3,3-tetramethyldisiloxane was produced. The structure of the product was also confirmed from the 1 H NMR spectrum (CDCl 3 , internal standard: tetramethylsilane) shown in FIG. 4 and the results of the elemental analysis below.
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, R1 is an alkylene group having 5 carbon atoms, R2 is a methyl group, and n is an average of 15) In a 2-liter four-necked round-bottomed flask equipped with a reflux tube, dropping funnel, stirring bar, and thermometer, polydimethylsiloxane having dimethylhydrosilyl groups at both ends (average composition formula: HMe 2 SiO (Me 2 SiO) 15 SiMe 2 H) and 100 mg of a divinyltetramethyldisiloxane solution of a divinyltetramethyldisiloxane platinum complex (platinum content: 2%) were added. The reaction solution in the flask was heated to 110° C. while stirring with a magnetic stirrer. Subsequently, 440 g of 1-chlorooct-7-ene was slowly added dropwise to the reaction solution. After the dropwise addition was completed, the reaction solution was stirred for 1 hour while maintaining the temperature at 110°C to 125°C. Unreacted 1-chlorooct-7-ene and the cyclic polydimethylsiloxane produced by the parallel reaction were distilled off under a reduced pressure of 0.2 kPa and a temperature of 145° C. in the flask. Filtration of the residue gave 1110 g of product. Figure 5 is the FT-IR spectrum of the isolated product. The Si-H absorption near 2100 cm -1 observed for 1,1,3,3-tetramethyldisiloxane and the olefin absorption near 1640 cm -1 observed for 1-chlorooct-7-ene are due to the formation It disappeared in the FT-IR spectrum of the product, and from this it was confirmed that the target product, dimethylpolysiloxane having chlorooctyl groups at both ends, had been 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, R1 is an alkylene group having 5 carbon atoms, R2 is a methyl group, and n is an average of 65) In a 500 ml four-necked round bottom flask equipped with a reflux tube, dropping funnel, stirring rod, and thermometer, polydimethylsiloxane having dimethylhydrosilyl groups at both ends (average composition formula: HMe 2 SiO (Me 2 SiO) 65 SiMe 2H ) and a solution of divinyltetramethyldisiloxane platinum complex in divinyltetramethyldisiloxane (platinum content: 2%) in an amount equivalent to 10 ppm based on 1-chlorooct-7-ene were added. The reaction solution in the flask was heated to 110° C. while stirring with a magnetic stirrer. Subsequently, 33.3 g of 1-chlorooct-7-ene was slowly added dropwise to the reaction solution. After the dropwise addition was completed, the reaction solution was stirred for 1 hour while maintaining the temperature at 110°C to 125°C. Unreacted 1-chlorooct-7-ene and the cyclic polydimethylsiloxane produced by the parallel reaction were distilled off under a reduced pressure of 0.2 kPa and a temperature of 145° C. in the flask. Filtration of the residue gave 290.3 g of product. Analysis of the product by FT-IR in the same manner as in Examples 1 and 2 confirmed that the desired product, 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, R1 is an alkylene group having 5 carbon atoms, R2 is a methyl group, and n is an average of 100) In a 500 ml four-necked round bottom flask equipped with a reflux tube, dropping funnel, stirring rod, and thermometer, polydimethylsiloxane having dimethylhydrosilyl groups at both ends (average compositional formula: HMe 2 SiO (Me 2 SiO) 100 SiMe 2H ) and a solution of divinyltetramethyldisiloxane platinum complex in divinyltetramethyldisiloxane (platinum content: 2%) in an amount equivalent to 10 ppm based on 1-chlorooct-7-ene were added. The reaction solution in the flask was heated to 110° C. while stirring with a magnetic stirrer. Subsequently, 21.9 g of 1-chlorooct-7-ene was slowly added dropwise to the reaction solution. After the dropwise addition was completed, the reaction solution was stirred for 1 hour while maintaining the temperature at 110°C to 125°C. Unreacted 1-chlorooct-7-ene and the cyclic polydimethylsiloxane produced by the parallel reaction were distilled off under a reduced pressure of 1 mmHg and a temperature of 150° C. in the flask. Filtration of the residue gave 266.3 g of product. Analysis of the product by FT-IR in the same manner as in Examples 1 and 2 confirmed that the desired product, dimethylpolysiloxane having chlorooctyl groups at both ends, was obtained.
Claims (1)
前記官能基が、アセトキシ基、又は（メタ）アクリロイルオキシ基である、
両末端官能性のシロキサン化合物を製造する方法であって、
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、前記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更に含む、方法。
The functional group is an acetoxy group or a (meth)acryloyloxy group,
A method for producing a siloxane compound having both terminal functionalities, the method comprising:
A method further comprising the step of producing the bishaloalkylsiloxane compound by a hydrosilylation reaction between a haloolefin compound represented by the following formula (2) and a siloxane compound represented by the following formula (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019135388A JP7350253B2 (en) | 2019-07-23 | 2019-07-23 | Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019135388A JP7350253B2 (en) | 2019-07-23 | 2019-07-23 | Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021017427A JP2021017427A (en) | 2021-02-15 |
| JP7350253B2 true JP7350253B2 (en) | 2023-09-26 |
Family
ID=74563028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019135388A Active JP7350253B2 (en) | 2019-07-23 | 2019-07-23 | Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7350253B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2770633A (en) * | 1953-10-28 | 1956-11-13 | Dow Corning | Organosilicon esters |
| LU84463A1 (en) * | 1982-11-10 | 1984-06-13 | Oreal | POLYQUATERNARY POLYSILOXANE POLYMERS |
| US5041593A (en) * | 1989-07-19 | 1991-08-20 | Dow Corning Corporation | Method for preparation of silyl functional fumarates |
| JP2688469B2 (en) * | 1993-03-31 | 1997-12-10 | 信越化学工業株式会社 | Method for producing (meth) acrylic functional group-containing organosilicon compound |
| KR101158767B1 (en) * | 2010-07-14 | 2012-06-22 | 주식회사 세원 | New imidazolium salts and electrolyte composition for dye-sensitized sollar cells containing the salt |
-
2019
- 2019-07-23 JP JP2019135388A patent/JP7350253B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021017427A (en) | 2021-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3616757B2 (en) | Cyclic silazane, process for its production and process for the production of bisaminoalkyl-terminated disiloxanes | |
| JPH06792B2 (en) | Method for producing hydrogen siloxane | |
| US5508369A (en) | Organopolysiloxanes having a silanol group and process of making them | |
| US5504235A (en) | Method for decomposing polysiloxane | |
| JP2612991B2 (en) | Method for chlorinating silicon compounds | |
| JPH054995A (en) | Organosilicon compound and production thereof | |
| JP2003532734A (en) | Preparation of secondary aminoisobutylalkoxysilanes | |
| JP7350253B2 (en) | Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities | |
| EP1149837B1 (en) | Organosilicon compounds | |
| JP5333971B2 (en) | Process for producing organosilicon compound containing β-cyanoester group | |
| US5239099A (en) | Azasilacycloalkyl functional alkoxysilanes and azasilacycloalkyl functional tetramethyldisiloxanes | |
| JP4344936B2 (en) | Method for producing organosilicon compound containing amino groups at both ends | |
| JP5913208B2 (en) | Novel fluorene compound and process for producing the same | |
| WO2007007597A1 (en) | Novel organosilicon compound and process for producing the same | |
| JP4433168B2 (en) | Organoxysilane compounds having protected hydroxyl groups | |
| JP3915883B2 (en) | Organosilicon compound | |
| JP4336970B2 (en) | Silane compound having protected carboxyl group and method for producing the same | |
| JP4543577B2 (en) | Organosilicon compound having protected catechol group and method for producing the same | |
| JP3856087B2 (en) | Method for producing 3-aminopropyl monoorganodiorganooxysilane | |
| JP4362690B2 (en) | Method for producing branched low-molecular siloxane | |
| US20180201633A1 (en) | Organosilicon compounds having (meth)acrylate groups and a process for preparation thereof | |
| JP4177316B2 (en) | Method for producing organosilane | |
| JPH0859837A (en) | Production of alkoxysilane | |
| JP4279066B2 (en) | Cyclic siloxane compound and method for producing the same | |
| US9139603B2 (en) | [3-(2-norbornyl)-2-norbornyl]silane compound and making method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220525 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230104 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230509 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230710 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230822 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230905 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7350253 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |