JP2688469B2 - Method for producing (meth) acrylic functional group-containing organosilicon compound - Google Patents

Method for producing (meth) acrylic functional group-containing organosilicon compound

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Publication number
JP2688469B2
JP2688469B2 JP7370693A JP7370693A JP2688469B2 JP 2688469 B2 JP2688469 B2 JP 2688469B2 JP 7370693 A JP7370693 A JP 7370693A JP 7370693 A JP7370693 A JP 7370693A JP 2688469 B2 JP2688469 B2 JP 2688469B2
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Japan
Prior art keywords
sio
meth
group
formula
organosilicon compound
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JP7370693A
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Japanese (ja)
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JPH06287305A (en
Inventor
秀好 柳澤
正明 山谷
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、（メタ）アクリル官能
基含有有機けい素化合物の新規な製造方法に関するもの
である。FIELD OF THE INVENTION The present invention relates to a novel method for producing a (meth) acrylic functional group-containing organosilicon compound.

【０００２】[0002]

【従来の技術】（メタ）アクリル官能基を含有するポリ
シロキサン化合物は、（メタ）アクリル官能基を含有す
るアルコキシシランまたはクロルシランを加水分解し、
縮合させる方法により合成されていた。この出発原料と
なる（メタ）アクリル官能基を含有するアルコキシシラ
ンまたはクロルシランの合成方法としては以下の２つの
方法が知られている。2. Description of the Related Art Polysiloxane compounds containing (meth) acrylic functional groups hydrolyze alkoxysilane or chlorosilane containing (meth) acrylic functional groups,
It was synthesized by the method of condensation. The following two methods are known as methods for synthesizing the alkoxysilane or chlorosilane having a (meth) acrylic functional group as the starting material.

【０００３】（１）（メタ）アクリル酸の塩化合物とク
ロルアルキルシランとを脱塩反応させて（メタ）アクリ
ル官能性シランを合成する方法。例えば、 CH2=CR1-COOM＋Cl(CH2)3Si(OCH3)3 →CH2=CR1-COO(CH2)
3Si(OCH3)3 （R1：-Hまたは-CH3、M ：１価金属） （２）アリル（メタ）アクリレートのような不飽和二重
結合を有する化合物とヒドロシランとを遷移金属化合物
の存在下に反応させるヒドロシリル化反応により（メ
タ）アクリル官能性シランを合成する方法。例えば、 CH2=CR1-COOCH2CH=CH2＋H-Si(OCH3)3 →CH2=CR1-COO(CH
2)3Si(OCH3)3 (1) A method of synthesizing a (meth) acrylic functional silane by desalting a salt compound of (meth) acrylic acid and chloroalkylsilane. For example, CH 2 = CR 1 -COOM + Cl (CH 2 ) 3 Si (OCH 3 ) 3 → CH 2 = CR 1 -COO (CH 2 )
3 Si (OCH 3 ) 3 (R 1 : —H or —CH 3 , M: a monovalent metal) (2) A transition metal compound containing a compound having an unsaturated double bond such as allyl (meth) acrylate and hydrosilane A method of synthesizing a (meth) acryl-functional silane by a hydrosilylation reaction in which the (meth) acryl-functional silane is reacted in the presence of. For example, CH 2 = CR 1 -COOCH 2 CH = CH 2 + H-Si (OCH 3 ) 3 → CH 2 = CR 1 -COO (CH
2 ) 3 Si (OCH 3 ) 3

【０００４】上記（１）の方法については種々提案され
ている。特公昭39-30271号公報には（メタ）アクリル酸
の第３級アミン塩を使用する方法が開示され、特公昭42
-23332号公報には（メタ）アクリル酸のアルカリ金属塩
と触媒として第３級アミン化合物あるいは第４級アンモ
ニウム塩を用いる方法が開示され、特開昭52-73826号公
報には（メタ）アクリル酸のアルカリ金属塩と触媒とし
て単環状ポリエーテルあるいは多環状ポリエーテルを使
用する方法が開示され、特開昭56-104890 号公報には
（メタ）アクリル酸のアルカリ金属塩と触媒として第４
級ホスホニウム塩を使用する方法が開示され、特開平3-
209388号公報には（メタ）アクリル酸のアルカリ金属塩
と触媒として特定構造の第４級アンモニウム塩を使用し
低温で反応させる方法が開示されている。一方、上記
（２）のヒドロシリル化反応による方法については特公
昭38-2136に開示されている。Various proposals have been made for the above method (1). JP-B-39-30271 discloses a method of using a tertiary amine salt of (meth) acrylic acid.
-23332 discloses a method using an alkali metal salt of (meth) acrylic acid and a tertiary amine compound or a quaternary ammonium salt as a catalyst, and JP-A-52-73826 discloses (meth) acrylic. A method of using an alkali metal salt of an acid and a monocyclic polyether or a polycyclic polyether as a catalyst is disclosed. JP-A-56-104890 discloses an alkali metal salt of (meth) acrylic acid and a catalyst as a catalyst.
A method of using a secondary phosphonium salt is disclosed, and JP-A-3-
Japanese Patent No. 209388 discloses a method in which an alkali metal salt of (meth) acrylic acid and a quaternary ammonium salt having a specific structure are used as a catalyst and reacted at a low temperature. On the other hand, the method (2) of hydrosilylation reaction is disclosed in JP-B-38-2136.

【０００５】[0005]

【発明が解決しようとする課題】しかし、上記（１）の
方法ではいずれも（メタ）アクリル酸のアルカリ金属塩
が固体で取扱いにくく、また、高価格であるため、（メ
タ）アクリル官能基含有シランは製造しにくく、高価格
であった。また、上記（２）の方法は製造方法としては
簡便であるが、特にアクリル酸系では原料のアリルアク
リレート等の不飽和二重結合含有アクリル酸エステルが
不安定で製造しにくいため高価であり、この方法も（メ
タ）アクリル官能基含有シランの価格が高いものであっ
た。このように原料シランまたはシランの原料が製造し
にくく高価であるため、従来の（メタ）アクリル官能基
含有シランを加水分解、縮合させる方法では得られるポ
リシロキサンが高価にならざるをえない。本発明は、こ
のような問題点がなく、有利に（メタ）アクリル官能基
含有有機けい素化合物を製造することのできる新規な製
造方法を提供しようとしてなされたものである。However, in any of the above methods (1), since the alkali metal salt of (meth) acrylic acid is solid and difficult to handle, and is expensive, it contains a (meth) acrylic functional group. Silane was difficult to manufacture and was expensive. In addition, the method (2) above is simple as a manufacturing method, but particularly in an acrylic acid type, an unsaturated double bond-containing acrylate ester such as allyl acrylate, which is a raw material, is unstable and difficult to manufacture, and thus expensive. Also in this method, the price of the silane containing a (meth) acrylic functional group was high. Since the raw material silane or the raw material of silane is difficult and expensive to produce, the polysiloxane obtained by the conventional method of hydrolyzing and condensing the (meth) acrylic functional group-containing silane must be expensive. The present invention has been made in an effort to provide a novel method for producing a (meth) acrylic functional group-containing organosilicon compound, which does not have such problems and can be advantageously produced.

【０００６】[0006]

【課題を解決するための手段】本発明者らは上記の課題
を解決するため鋭意検討の結果、（メタ）アクリル酸と
ハロアルキル官能性有機けい素化合物とを１，８−ジア
ザビシクロ［５．４．０］ウンデセン−７の存在下に反
応させる方法により目的が達成できることを見出して本
発明に至った。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that (meth) acrylic acid and a haloalkyl-functional organosilicon compound are combined with 1,8-diazabicyclo [5.4]. .0] The present invention has been completed by finding that the object can be achieved by a method of reacting in the presence of undecene-7.

【０００７】すなわち、本発明は、（ａ）（メタ）アク
リル酸（Ｉ） CH2=CR1-COOH ・・・（Ｉ） （式中、R1はメチル基または水素原子を示す。）と
（ｂ）平均組成式（II） (XR2)k(CH3)m(R3)nSiO(4-k-m-n)/2 ・・・（II） （式中、Ｘはハロゲンを示し、R2は炭素数１以上の２価
炭化水素基を示し、R3は炭素数１以上の１価有機基を示
し、ｋ＋ｍ＋ｎ≦４、０＜ｋ≦４、０≦ｍ＜４、０≦ｎ
＜４である。）で表されるハロアルキル官能性有機けい
素化合物とを（ｃ）１，８−ジアザビシクロ［５．４．
０］ウンデセン−７の存在下に反応させることを特徴と
する、平均組成式 (III) (CH2=CR1-COOR2)k(CH3)m(R3)nSiO(4-k-m-n)/2 ・・・(III) （式中、R1はメチル基または水素原子を示し、R2は炭素
数１以上の２価炭化水素基を示し、R3は炭素数１以上の
１価有機基を示し、ｋ＋ｍ＋ｎ≦４、０＜ｋ≦４、０≦
ｍ＜４、０≦ｎ＜４である。）で表される（メタ）アク
リル官能基含有有機けい素化合物の製造方法、を要旨と
するものである。That is, according to the present invention, (a) (meth) acrylic acid (I) CH 2 = CR 1 -COOH (I) (wherein R 1 represents a methyl group or a hydrogen atom). (B) Average composition formula (II) (XR 2 ) k (CH 3 ) m (R 3 ) n SiO (4-kmn) / 2 (II) (In the formula, X represents halogen and R 2 Represents a divalent hydrocarbon group having 1 or more carbon atoms, R 3 represents a monovalent organic group having 1 or more carbon atoms, k + m + n ≦ 4, 0 <k ≦ 4, 0 ≦ m <4, 0 ≦ n
<4. ) And a haloalkyl-functional organosilicon compound represented by the formula (c) 1,8-diazabicyclo [5.4.
[0] Undecene-7 in the presence of an average compositional formula (III) (CH 2 = CR 1 -COOR 2 ) k (CH 3 ) m (R 3 ) n SiO (4-kmn) / 2 ··· (III) (wherein, R 1 represents a methyl group or a hydrogen atom, R 2 represents one or more divalent hydrocarbon group having a carbon number, R 3 is a monovalent organic one or more carbon atoms A group, k + m + n ≦ 4, 0 <k ≦ 4, 0 ≦
m <4 and 0 ≦ n <4. And a method for producing a (meth) acrylic functional group-containing organosilicon compound represented by the formula (1).

【０００８】以下に本発明について詳しく説明する。本
発明の製造方法においては、上記の反応原料（ａ）およ
び（ｂ）という入手が容易で安価な原料を使用し、温和
な条件で有利に反応を行うことができる。これには１，
８−ジアザビシクロ［５．４．０］ウンデセン−７（以
下ＤＢＵと略す）の使用が重要である。このＤＢＵは原
料（ａ）と（ｂ）が反応する際にハロゲン化水素捕捉剤
として働くのであるが、ＤＢＵを用いることにより80℃
〜100 ℃という低温で反応を完結させることができる。
また、生成するＤＢＵ塩が大径の粗粒状となるので濾別
が極めて容易であり、前述した（メタ）アクリル酸の塩
とクロルアルキルシランとを脱塩反応させる場合の生成
塩の除去と比較して作業性に優れている。さらに、使用
したＤＢＵはほぼ定量的に回収できるのでコストも低く
抑えることができる。Hereinafter, the present invention will be described in detail. In the production method of the present invention, the reaction raw materials (a) and (b), which are easily available and inexpensive, are used, and the reaction can be advantageously performed under mild conditions. This is 1,
The use of 8-diazabicyclo [5.4.0] undecene-7 (hereinafter abbreviated as DBU) is important. This DBU acts as a hydrogen halide scavenger when the raw materials (a) and (b) react with each other.
The reaction can be completed at a low temperature of -100 ° C.
Further, since the produced DBU salt becomes large-sized coarse particles, it is extremely easy to separate by filtration, and compared with the removal of the produced salt in the case where the salt of (meth) acrylic acid and chloroalkylsilane are desalted. And has excellent workability. Further, since the used DBU can be collected almost quantitatively, the cost can be kept low.

【０００９】反応原料（ａ）の（メタ）アクリル酸は一
般に市販されているものを使用することができ、必要に
応じて硫酸ナトリウム、硫酸マグネシウム、モレキュラ
ーシーブスなどの脱水剤を用いて脱水してから使用して
もよい。As the (meth) acrylic acid as the reaction raw material (a), commercially available products can be used. If necessary, the (meth) acrylic acid can be dehydrated by using a dehydrating agent such as sodium sulfate, magnesium sulfate and molecular sieves. It may be used from.

【００１０】反応原料（ｂ）のハロアルキル官能性有機
けい素化合物は平均組成式 (XR2)k(CH3)m(R3)nSiO(4-k-m-n)/2 で示される。式中のＸはハロゲン原子を示し、Cl、Brが
好適である。R2は炭素数１以上の２価の炭化水素基を示
し、例えば-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2
-、-(CH2)6-、-(CH2)10-、-CH2CH(CH3)CH2-、-(CH2)14- 等
があげられる。R3は炭素数１以上の有機基を示し、例え
ばCH3CH2-、CH3CH2CH2-、CH3(CH2)3-、CH3(CH2)5-、CH3(C
H2)9-、H2N(CH2)2NH(CH2)3-、H2N(CH2)3-、HS(CH2)3-、[0010] represented by haloalkyl-functional organosilicon compound in the reaction raw material (b) has an average composition formula (XR 2) k (CH 3 ) m (R 3) n SiO (4-kmn) / 2. X in the formula represents a halogen atom, and Cl and Br are preferable. R 2 represents a divalent hydrocarbon group having 1 or more carbon atoms, for example, —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2
-, - (CH 2) 6 -, - (CH 2) 10 -, - CH 2 CH (CH 3) CH 2 -, - (CH 2) 14 - , and the like. R 3 represents an organic group having 1 or more carbon atoms, such as CH 3 CH 2 —, CH 3 CH 2 CH 2 —, CH 3 (CH 2 ) 3 —, CH 3 (CH 2 ) 5 —, CH 3 (C
H 2 ) 9- , H 2 N (CH 2 ) 2 NH (CH 2 ) 3- , H 2 N (CH 2 ) 3- , HS (CH 2 ) 3- ,

【化１】 R4(OCH2CH2)11OCH2CH2CH2-、 R4(OCH2CH2)8[OCH(CH3)C
H2]3OCH2CH2CH2-、R4OCOR5-、R4COOR5-、R4O-（R4は炭素数
１以上の１価の炭化水素基、R5は炭素数１以上の２価の
炭化水素基を示す。）等があげられる。Embedded image R 4 (OCH 2 CH 2 ) 11 OCH 2 CH 2 CH 2- , R 4 (OCH 2 CH 2 ) 8 [OCH (CH 3 ) C
H 2 ] 3 OCH 2 CH 2 CH 2- , R 4 OCOR 5- , R 4 COOR 5- , R 4 O- (R 4 is a monovalent hydrocarbon group having 1 or more carbon atoms, R 5 is 1 carbon atom The above-mentioned divalent hydrocarbon groups are shown) and the like.

【００１１】上記平均組成式を満足する具体例としては
以下のものがあげられる。ただし、１分子中のシロキサ
ン単位の数は平均値を示す。 {Cl(CH2)3}(CH3)2SiOSi(CH3)2{(CH2)3Cl}、 {Cl(CH2)3}(CH3)2SiO{(CH3)2SiO}4Si(CH3)2{(CH2)3Cl}、 (CH3)3SiO{Cl(CH2)3CH3SiO}3{(CH3)2SiO}2Si(CH3)3、 {Cl(CH2)3}(CH3)2SiO[{Cl(CH2)3}CH3SiO]8Si(CH3)2{(CH
2)3Cl}、The following are specific examples which satisfy the above average composition formula. However, the number of siloxane units in one molecule represents an average value. {Cl (CH 2) 3} (CH 3) 2 SiOSi (CH 3) 2 {(CH 2) 3 Cl}, {Cl (CH 2) 3} (CH 3) 2 SiO {(CH 3) 2 SiO} 4 Si (CH 3 ) 2 {(CH 2 ) 3 Cl}, (CH 3 ) 3 SiO {Cl (CH 2 ) 3 CH 3 SiO} 3 {(CH 3 ) 2 SiO} 2 Si (CH 3 ) 3 , {Cl (CH 2 ) 3 } (CH 3 ) 2 SiO [{Cl (CH 2 ) 3 } CH 3 SiO] 8 Si (CH 3 ) 2 {(CH
2 ) 3 Cl},

【化２】 Embedded image

【００１２】{Br(CH2)3}(CH3)2SiOSi(CH3)2{(CH2)3Br}、 {Br(CH2)3}(CH3)2SiO{(CH3)2SiO}4Si(CH3)2{(CH2)3Br}、 (CH3)3SiO[{Br(CH2)3}CH3SiO]20Si(CH3)3、 (CH3)3SiO[{Br(CH2)3}CH3SiO]5{(CH3)2SiO}10Si(CH3)3、 {Br(CH2)3}(CH3)2SiO[{Br(CH2)3}CH3SiO]3{(CH3)2SiO}
10Si(CH3)2{(CH2)3Br}、 {Br(CH2)3}(CH3)2SiO{(C6H13)CH3SiO}5[{Br(CH2)3}CH3S
iO]5※ ※Si(CH3)2{(CH2)3Br}、 （※印の間は SiOSi結合により結合していることを示
す。以下同様。）{Br (CH 2 ) 3 } (CH 3 ) 2 SiOSi (CH 3 ) 2 {(CH 2 ) 3 Br}, {Br (CH 2 ) 3 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 4 Si (CH 3 ) 2 {(CH 2 ) 3 Br}, (CH 3 ) 3 SiO [{Br (CH 2 ) 3 } CH 3 SiO] 20 Si (CH 3 ) 3 , (CH 3 ). 3 SiO [{Br (CH 2 ) 3 } CH 3 SiO] 5 {(CH 3 ) 2 SiO} 10 Si (CH 3 ) 3 , {Br (CH 2 ) 3 } (CH 3 ) 2 SiO [{Br ( CH 2 ) 3 } CH 3 SiO] 3 {(CH 3 ) 2 SiO}
10 Si (CH 3) 2 { (CH 2) 3 Br}, {Br (CH 2) 3} (CH 3) 2 SiO {(C 6 H 13) CH 3 SiO} 5 [{Br (CH 2) 3 } CH 3 S
iO] 5 * * Si (CH 3 ) 2 {(CH 2 ) 3 Br}, (The space between * indicates that they are bonded by SiOSi bonds. The same applies below.)

【化３】 Embedded image

【００１３】(ClCH2)(CH3)2SiOSi(CH3)2(CH2Cl)、 (ClCH2)(CH3)2SiO{(CH3)2SiO}4Si(CH3)2(CH2Cl)、 (CH3)3SiO{(ClCH2)CH3SiO}10Si(CH3)3、 (CH3)3SiO{(CH3)2SiO}10{(ClCH2)CH3SiO}5Si(CH3)3、 (ClCH2)(CH3)2SiO{(CH3)2SiO}10{(ClCH2)CH3SiO}3Si(CH
3)2(CH2Cl)、 (ClCH2)(CH3)2SiO{(ClCH2)CH3SiO}5Si(CH3)2(CH2Cl)、 {(ClCH2)(CH3)2SiO}4Si、 [(ClCH2)(CH3)2SiO{(CH3)2Si
O}4]4Si、 [(ClCH2)(CH3)2SiO{(CH3)2SiO}10{(ClCH2)CH3SiO}2]4S
i、(ClCH 2 ) (CH 3 ) 2 SiOSi (CH 3 ) 2 (CH 2 Cl), (ClCH 2 ) (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 4 Si (CH 3 ) 2 ( CH 2 Cl), (CH 3 ) 3 SiO {(ClCH 2) CH 3 SiO} 10 Si (CH 3) 3, (CH 3) 3 SiO {(CH 3) 2 SiO} 10 {(ClCH 2) CH 3 SiO} 5 Si (CH 3) 3, (ClCH 2) (CH 3) 2 SiO {(CH 3) 2 SiO} 10 {(ClCH 2) CH 3 SiO} 3 Si (CH
3 ) 2 (CH 2 Cl), (ClCH 2 ) (CH 3 ) 2 SiO {(ClCH 2 ) CH 3 SiO} 5 Si (CH 3 ) 2 (CH 2 Cl), {(ClCH 2 ) (CH 3 ) 2 SiO} 4 Si, ((ClCH 2 ) (CH 3 ) 2 SiO {(CH 3 ) 2 Si
O} 4 ] 4 Si, [(ClCH 2 ) (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 10 {(ClCH 2 ) CH 3 SiO} 2 ] 4 S
i,

【００１４】[0014]

【化４】 (CH3)3SiO{(ClCH2)CH3SiO}4{(C6H13)CH3SiO}4Si(CH3)3、 (CH3)3SiO{(ClCH2)CH3SiO}5{(CH3)2SiO}10{(C6H13)CH3S
iO}5Si(CH3)3、 (CH3)3SiO{(ClCH2)CH3SiO}2{(C10H21)CH3SiO}4Si(C
H3)3、 (CH3)3SiO{(ClCH2)CH3SiO}4{(CH3)2SiO}4{(C10H21)CH3S
iO}4Si(CH3)3、Embedded image (CH 3) 3 SiO {( ClCH 2) CH 3 SiO} 4 {(C 6 H 13) CH 3 SiO} 4 Si (CH 3) 3, (CH 3) 3 SiO {(ClCH 2) CH 3 SiO} 5 {(CH 3 ) 2 SiO} 10 {(C 6 H 13 ) CH 3 S
iO} 5 Si (CH 3 ) 3 , (CH 3 ) 3 SiO {(ClCH 2 ) CH 3 SiO} 2 {(C 10 H 21 ) CH 3 SiO} 4 Si (C
H 3) 3, (CH 3 ) 3 SiO {(ClCH 2) CH 3 SiO} 4 {(CH 3) 2 SiO} 4 {(C 10 H 21) CH 3 S
iO} 4 Si (CH 3 ) 3 ,

【００１５】{Br(CH2)3}(CH3)2SiO[{Br(CH2)3}CH3SiO]4
Si(CH3)2{(CH2)3Br}、 {Br(CH2)3}(CH3)2SiO{(CH3)2SiO}4Si(CH3)2{(CH2)3Br}、 {Br(CH2)3}(CH3)2SiO[{Br(CH2)3}CH3SiO]20{(CH3)2SiO}
40※ ※{(C6H13)CH3SiO}20Si(CH3)2{(CH2)3Br}、 {Br(CH2)6}(CH3)2SiO[{Br(CH2)6}CH3SiO]4Si(CH3)2{(CH
2)6Br}、 {Br(CH2)6}(CH3)2SiO[{Br(CH2)6}CH3SiO}4{(CH3)2SiO}8
Si(CH3)2{(CH2)6Br}、 (CH3)3SiO[{Br(CH2)6}CH3SiO]10Si(CH3)3、 (CH3)3SiO[{Br(CH2)6}CH3SiO]5{(CH3)2SiO}10Si(CH3)3、 (CH3)3SiO[{Br(CH2)10}CH3SiO]10Si(CH3)3、 (CH3)3SiO[{Br(CH2)10}CH3SiO}5{(CH3)2SiO}10Si(C
H3)3、{Br (CH 2 ) 3 } (CH 3 ) 2 SiO [{Br (CH 2 ) 3 } CH 3 SiO] 4
Si (CH 3) 2 {( CH 2) 3 Br}, {Br (CH 2) 3} (CH 3) 2 SiO {(CH 3) 2 SiO} 4 Si (CH 3) 2 {(CH 2) 3 Br}, {Br (CH 2 ) 3 } (CH 3 ) 2 SiO [{Br (CH 2 ) 3 } CH 3 SiO] 20 {(CH 3 ) 2 SiO}
40 * * {(C 6 H 13 ) CH 3 SiO} 20 Si (CH 3 ) 2 {(CH 2 ) 3 Br}, {Br (CH 2 ) 6 } (CH 3 ) 2 SiO [{Br (CH 2 ) 6 } CH 3 SiO] 4 Si (CH 3 ) 2 {(CH
2 ) 6 Br}, {Br (CH 2 ) 6 } (CH 3 ) 2 SiO [{Br (CH 2 ) 6 } CH 3 SiO} 4 {(CH 3 ) 2 SiO} 8
Si (CH 3) 2 {( CH 2) 6 Br}, (CH 3) 3 SiO [{Br (CH 2) 6} CH 3 SiO] 10 Si (CH 3) 3, (CH 3) 3 SiO [{ Br (CH 2 ) 6 } CH 3 SiO] 5 {(CH 3 ) 2 SiO} 10 Si (CH 3 ) 3 , (CH 3 ) 3 SiO [{Br (CH 2 ) 10 } CH 3 SiO] 10 Si ( CH 3) 3, (CH 3 ) 3 SiO [{Br (CH 2) 10} CH 3 SiO} 5 {(CH 3) 2 SiO} 10 Si (C
H 3 ) 3 ,

【００１６】[0016]

【化５】 Embedded image

【００１７】また、ハロゲン化水素（ＨＸ）の捕捉剤と
しては前記のとおりＤＢＵを使用する。本発明のよう
に、特にハロアルキル官能性有機けい素化合物と（メ
タ）アクリル酸とを反応させる系においてＤＢＵを使用
すると、反応速度が増加し、著しく収率が向上すること
はこれまで知られていなかった。このＤＢＵは副次的に
生成する塩が粒径の大きい粗粒状であるため濾過性に優
れる利点もある。さらに、このＤＢＵの塩からはNaOHや
KOH などのアルカリ性物質により容易に且つほぼ定量的
にＤＢＵが回収できるという利点もあるため、本発明に
おけるような反応系でのＨＸの捕捉剤として適してい
る。As described above, DBU is used as a scavenger for hydrogen halide (HX). It has been known so far that when DBU is used in a system in which a haloalkyl-functional organosilicon compound is reacted with (meth) acrylic acid, as in the present invention, the reaction rate is increased and the yield is remarkably improved. There wasn't. This DBU also has an advantage in that it has excellent filterability because the salt produced as a by-product is coarse particles having a large particle size. Furthermore, from this DBU salt,
Since it has an advantage that DBU can be easily and almost quantitatively recovered by an alkaline substance such as KOH, it is suitable as a scavenger for HX in the reaction system of the present invention.

【００１８】各反応原料のモル比は、ハロアルキルシロ
キサン化合物のハロアルキル基 1.0モルに対し、（メ
タ）アクリル酸は 0.1〜2.0 モル、好適には 0.5〜1.5
モル使用し、ＨＸ捕捉剤は 0.1〜2.0 モル、好適には
0.5〜1.5 モル使用し反応させるのが良い。次に、反応
温度は30〜150 ℃の範囲であれば良く、さらに50〜130
℃の範囲がより好ましい。The molar ratio of each reaction raw material is such that (meth) acrylic acid is 0.1 to 2.0 moles, preferably 0.5 to 1.5 moles, relative to 1.0 mole of the haloalkyl group of the haloalkylsiloxane compound.
Moles, the HX scavenger is 0.1 to 2.0 moles, preferably
It is advisable to use 0.5 to 1.5 mol to react. Next, the reaction temperature may be in the range of 30 to 150 ° C, and further 50 to 130 ° C.
The range of ° C is more preferable.

【００１９】反応を行うに際しては、種々の溶剤を使用
することが可能で、例えば、ベンゼン、トルエン、キシ
レン等の芳香族系炭化水素類、ヘキサン、ペンタン、オ
クタン、デカン等の脂肪族炭化水素類、塩化メチレン、
クロロホルム、四塩化炭素等の塩素系溶剤、メタノー
ル、エタノール等のアルコール類、酢酸エチル、酢酸メ
チル等のエステル類、ジエチルエーテル、ジブチルエー
テル、テトラヒドロフラン、ジオキサン等のエーテル
類、ジメチルホルムアミド等のアミド類、メチルエチル
ケトン、ジエチルケトン、メチルイソブチルケトン等の
ケトン類など、種々のものが使用可能である。In carrying out the reaction, various solvents can be used, for example, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane, pentane, octane and decane. , Methylene chloride,
Chloroform, chlorine-based solvents such as carbon tetrachloride, alcohols such as methanol and ethanol, esters such as ethyl acetate and methyl acetate, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, amides such as dimethylformamide, Various substances such as ketones such as methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone can be used.

【００２０】また、反応時に重合防止のため従来公知の
種々の重合禁止剤、例えば、メトキシフェノール、2,6-
ジ−t-ブチル−4-メチルフェノール等に代表されるフェ
ノール系化合物、N,N'−ジフェニルジアミノベンゼン等
のアミン系化合物、含硫黄化合物などを添加してもよ
い。In order to prevent polymerization during the reaction, various conventionally known polymerization inhibitors such as methoxyphenol and 2,6-
A phenol compound represented by di-t-butyl-4-methylphenol, an amine compound such as N, N'-diphenyldiaminobenzene, a sulfur-containing compound, etc. may be added.

【００２１】前述のような本発明の方法により製造され
る（メタ）アクリル基含有有機けい素化合物は、前記平
均組成式 (CH2=CR1-COOR2)k(CH3)m(R3)nSiO(4-k-m-n)/2
で表され、式中のR1〜R3等は前記のとおりである。この
ような化合物の例として以下のものがあげられる。ただ
し、１分子中のシロキサン単位の数は平均値を示す。The (meth) acrylic group-containing organosilicon compound produced by the method of the present invention as described above has the above average composition formula (CH 2 = CR 1 -COOR 2 ) k (CH 3 ) m (R 3 ) n SiO (4-kmn) / 2
And R 1 to R 3 and the like in the formula are as described above. Examples of such compounds include the following. However, the number of siloxane units in one molecule represents an average value.

【００２２】{CH2=C(CH3)COO(CH2)3}(CH3)2SiOSi(CH3)2
{(CH2)3OOCC(CH3)=CH2}、 {CH2=C(CH3)COO(CH2)3}(CH3)2SiO{(CH3)2SiO}4※ ※Si(CH3)2{(CH2)3OOCC(CH3)=CH2}、 (CH3)3SiO[{CH2=C(CH3)COO(CH2)3}CH3SiO]3{(CH3)2SiO}
2Si(CH3)3、 {CH2=C(CH3)COO(CH2)3}(CH3)2SiO[{CH2=C(CH3)COO(CH2)
3}CH3SiO]8※ ※Si(CH3)2{(CH2)3OOCC(CH3)=CH2}、 {CH2=C(CH3)COO(CH2)3}(CH3)2SiO{(C6H13)CH3SiO}5※ ※[{CH2=C(CH3)COO(CH2)3}CH3SiO]5Si(CH3)2{(CH2)3OOC
C(CH3)=CH2}、{CH 2 = C (CH 3 ) COO (CH 2 ) 3 } (CH 3 ) 2 SiOSi (CH 3 ) 2
{(CH 2 ) 3 OOCC (CH 3 ) = CH 2 }, {CH 2 = C (CH 3 ) COO (CH 2 ) 3 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 4 ※※ Si (CH 3 ) 2 {(CH 2 ) 3 OOCC (CH 3 ) = CH 2 }, (CH 3 ) 3 SiO [{CH 2 = C (CH 3 ) COO (CH 2 ) 3 } CH 3 SiO] 3 { (CH 3 ) 2 SiO}
2 Si (CH 3) 3, {CH 2 = C (CH 3) COO (CH 2) 3} (CH 3) 2 SiO [{CH 2 = C (CH 3) COO (CH 2)
3 } CH 3 SiO] 8 * * Si (CH 3 ) 2 {(CH 2 ) 3 OOCC (CH 3 ) = CH 2 }, {CH 2 = C (CH 3 ) COO (CH 2 ) 3 } (CH 3 ) 2 SiO {(C 6 H 13 ) CH 3 SiO} 5 * * [{CH 2 = C (CH 3 ) COO (CH 2 ) 3 } CH 3 SiO] 5 Si (CH 3 ) 2 {(CH 2 ). 3 OOC
C (CH 3 ) = CH 2 },

【００２３】[0023]

【化６】 Embedded image

【００２４】{CH2=CHCOO(CH2)3}(CH3)2SiOSi(CH3)2{(CH
2)3OOCCH=CH2}、 {CH2=CHCOO(CH2)3}(CH3)2SiO{(CH3)2SiO}4Si(CH3)2{(CH
2)3OOCCH=CH2}、 (CH3)3SiO[{CH2=CHCOO(CH2)3}CH3SiO]3{(CH3)2SiO}2Si
(CH3)3、 {CH2=CHCOO(CH2)3}(CH3)2SiO{(C6H13)CH3SiO}5※ ※[{CH2=CHCOO(CH2)3}CH3SiO]5Si(CH3)2{(CH2)3OOCCH=C
H2}、{CH 2 = CHCOO (CH 2 ) 3 } (CH 3 ) 2 SiOSi (CH 3 ) 2 {(CH
2 ) 3 OOCCH = CH 2 }, {CH 2 = CHCOO (CH 2 ) 3 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 4 Si (CH 3 ) 2 {(CH
2 ) 3 OOCCH = CH 2 }, (CH 3 ) 3 SiO [{CH 2 = CHCOO (CH 2 ) 3 } CH 3 SiO] 3 {(CH 3 ) 2 SiO} 2 Si
(CH 3 ) 3 , {CH 2 = CHCOO (CH 2 ) 3 } (CH 3 ) 2 SiO {(C 6 H 13 ) CH 3 SiO} 5 * * [{CH 2 = CHCOO (CH 2 ) 3 } CH 3 SiO] 5 Si (CH 3 ) 2 {(CH 2 ) 3 OOCCH = C
H 2 },

【化７】 Embedded image

【００２５】{CH2=C(CH3)COOCH2}(CH3)2SiOSi(CH3)2{CH
2OOCC(CH3)=CH2}、 {CH2=C(CH3)COOCH2}(CH3)2SiO{(CH3)2SiO}4Si(CH3)2{CH
2OOCC(CH3)=CH2}、 (CH3)3SiO[{CH2=C(CH3)COOCH2}CH3SiO]10Si(CH3)3、 (CH3)3SiO{(CH3)2SiO}10[{CH2=C(CH3)COOCH2}CH3SiO]5S
i(CH3)3、 {CH2=C(CH3)COOCH2}(CH3)2SiO{(CH3)2SiO}10※ ※[{CH2=C(CH3)COOCH2}CH3SiO]3Si(CH3)2{CH2OOCC(CH3)
=CH2}、 {CH2=C(CH3)COOCH2}(CH3)2SiO[{CH2=C(CH3)COOCH2}CH3S
iO]5※ ※Si(CH3)2{CH2OOCC(CH3)=CH2}、 [{CH2=C(CH3)COOCH2}(CH3)2SiO]4Si、 [{CH2=C(CH3)COOCH2}(CH3)2SiO{(CH3)2SiO}4]4Si、 (CH3)3SiO[{CH2=C(CH3)COOCH2}CH3SiO]4{(C6H13)CH3Si
O}4Si(CH3)3、 (CH3)3SiO[{CH2=C(CH3)COOCH2}CH3SiO]5{(CH3)2SiO}10
※ ※{(C6H13)CH3SiO}5Si(CH3)3、 (CH3)3SiO[{CH2=C(CH3)COOCH2}CH3SiO]2{(C10H21)CH3Si
O}4Si(CH3)3、 (CH3)3SiO[{CH2=C(CH3)COOCH2}CH3SiO]4{(CH3)2SiO}4※ ※{(C10H21)CH3SiO}4Si(CH3)3、{CH 2 = C (CH 3 ) COOCH 2 } (CH 3 ) 2 SiOSi (CH 3 ) 2 {CH
2 OOCC (CH 3 ) = CH 2 }, {CH 2 = C (CH 3 ) COOCH 2 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 4 Si (CH 3 ) 2 {CH
2 OOCC (CH 3 ) = CH 2 }, (CH 3 ) 3 SiO [{CH 2 = C (CH 3 ) COOCH 2 } CH 3 SiO] 10 Si (CH 3 ) 3 , (CH 3 ) 3 SiO {( CH 3 ) 2 SiO} 10 [{CH 2 = C (CH 3 ) COOCH 2 } CH 3 SiO] 5 S
i (CH 3 ) 3 , {CH 2 = C (CH 3 ) COOCH 2 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 10 * * [{CH 2 = C (CH 3 ) COOCH 2 } CH 3 SiO] 3 Si (CH 3 ) 2 {CH 2 OOCC (CH 3 )
= CH 2 }, {CH 2 = C (CH 3 ) COOCH 2 } (CH 3 ) 2 SiO [{CH 2 = C (CH 3 ) COOCH 2 } CH 3 S
iO] 5 * * Si (CH 3 ) 2 {CH 2 OOCC (CH 3 ) = CH 2 }, [{CH 2 = C (CH 3 ) COOCH 2 } (CH 3 ) 2 SiO] 4 Si, [{CH 2 = C (CH 3 ) COOCH 2 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 4 ] 4 Si, (CH 3 ) 3 SiO [{CH 2 = C (CH 3 ) COOCH 2 } CH 3 SiO] 4 {(C 6 H 13 ) CH 3 Si
O} 4 Si (CH 3) 3, (CH 3) 3 SiO [{CH 2 = C (CH 3) COOCH 2} CH 3 SiO] 5 {(CH 3) 2 SiO} 10
※ ※ {(C 6 H 13 ) CH 3 SiO} 5 Si (CH 3) 3, (CH 3) 3 SiO [{CH 2 = C (CH 3) COOCH 2} CH 3 SiO] 2 {(C 10 H 21 ) CH 3 Si
O} 4 Si (CH 3 ) 3 , (CH 3 ) 3 SiO [{CH 2 = C (CH 3 ) COOCH 2 } CH 3 SiO] 4 {(CH 3 ) 2 SiO} 4 ※※ {(C 10 H 21 ) CH 3 SiO} 4 Si (CH 3 ) 3 ,

【００２６】[0026]

【化８】 ．Embedded image .

【００２７】 (CH2=CHCOOCH2)(CH3)2SiOSi(CH3)2(CH2OOCCH=CH2)、 (CH2=CHCOOCH2)(CH3)2SiO{(CH3)2SiO}4Si(CH3)2(CH2OOC
CH=CH2)、 (CH3)3SiO{(CH2=CHCOOCH2)CH3SiO}10Si(CH3)3、 (CH3)3SiO{(CH3)2SiO}10{(CH2=CHCOOCH2)CH3SiO}5Si(CH
3)3、 (CH2=CHCOOCH2)(CH3)2SiO{(CH3)2SiO}10{(CH2=CHCOOC
H2)CH3SiO}3 ※ ※Si(CH3)2(CH2OOCCH=CH2)、 (CH2=CHCOOCH2)(CH3)2SiO{(CH2=CHCOOCH2)CH3SiO}5Si(C
H3)2(CH2OOCCH=CH2)、 {(CH2=CHCOOCH2)(CH3)2SiO}4Si、 [{(CH2=CHCOOCH2)(CH3)2SiO}{(CH3)2SiO}4]4Si、 (CH3)3SiO{(CH2=CHCOOCH2)CH3SiO}4{(C6H13)CH3SiO}4Si
(CH3)3、 (CH3)3SiO{(CH2=CHCOOCH2)CH3SiO}5{(CH3)2SiO}10{(C6H
13)CH3SiO}5 ※ ※Si(CH3)3、 (CH3)3SiO{(CH2=CHCOOCH2)CH3SiO}2{(C10H21)CH3SiO}4S
i(CH3)3、 (CH3)3SiO{(CH2=CHCOOCH2)CH3SiO]4{(CH3)2SiO}4{(C10H
21)CH3SiO}4 ※ ※Si(CH3)3、(CH 2 = CHCOOCH 2 ) (CH 3 ) 2 SiOSi (CH 3 ) 2 (CH 2 OOCCH = CH 2 ), (CH 2 = CHCOOCH 2 ) (CH 3 ) 2 SiO {(CH 3 ) 2 SiO } 4 Si (CH 3 ) 2 (CH 2 OOC
CH = CH 2), (CH 3) 3 SiO {(CH 2 = CHCOOCH 2) CH 3 SiO} 10 Si (CH 3) 3, (CH 3) 3 SiO {(CH 3) 2 SiO} 10 {(CH 2 = CHCOOCH 2 ) CH 3 SiO} 5 Si (CH
3 ) 3 , (CH 2 = CHCOOCH 2 ) (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 10 {(CH 2 = CHCOOC
H 2 ) CH 3 SiO} 3 * * Si (CH 3 ) 2 (CH 2 OOCCH = CH 2 ), (CH 2 = CHCOOCH 2 ) (CH 3 ) 2 SiO {(CH 2 = CHCOOCH 2 ) CH 3 SiO} 5 Si (C
H 3) 2 (CH 2 OOCCH = CH 2), {(CH 2 = CHCOOCH 2) (CH 3) 2 SiO} 4 Si, [{(CH 2 = CHCOOCH 2) (CH 3) 2 SiO} {(CH 3 ) 2 SiO} 4 ] 4 Si, (CH 3 ) 3 SiO {(CH 2 = CHCOOCH 2 ) CH 3 SiO} 4 {(C 6 H 13 ) CH 3 SiO} 4 Si
(CH 3) 3, (CH 3) 3 SiO {(CH 2 = CHCOOCH 2) CH 3 SiO} 5 {(CH 3) 2 SiO} 10 {(C 6 H
13 ) CH 3 SiO} 5 * * Si (CH 3 ) 3 , (CH 3 ) 3 SiO {(CH 2 = CHCOOCH 2 ) CH 3 SiO} 2 {(C 10 H 21 ) CH 3 SiO} 4 S
i (CH 3 ) 3 , (CH 3 ) 3 SiO {(CH 2 = CHCOOCH 2 ) CH 3 SiO] 4 {(CH 3 ) 2 SiO} 4 {(C 10 H
21 ) CH 3 SiO} 4 * * Si (CH 3 ) 3 ,

【００２８】[0028]

【化９】 Embedded image

【００２９】[0029]

【化１０】 Embedded image

【００３０】 (CH3)3SiO[{CH2=C(CH3)COO(CH2)6}CH3SiO]10Si(CH3)3、 (CH3)3SiO[{CH2=C(CH3)COO(CH2)6}CH3SiO]5{(CH3)2SiO}
10Si(CH3)3、 (CH3)3SiO[{CH2=C(CH3)COO(CH2)10}CH3SiO]10Si(CH3)3、 (CH3)3SiO[{CH2=C(CH3)COO(CH2)10}CH3SiO]5{(CH3)2Si
O}10Si(CH3)3、 (CH3)3SiO[{CH2=CHCOO(CH2)6}CH3SiO]10Si(CH3)3、 (CH3)3SiO[{CH2=CHCOO(CH2)6}CH3SiO]5{(CH3)2SiO}10Si
(CH3)3、 (CH3)3SiO[{CH2=CHCOO(CH2)10}CH3SiO]10Si(CH3)3、 (CH3)3SiO[{CH2=CHCOO(CH2)10}CH3SiO]5{(CH3)2SiO}10S
i(CH3)3、(CH 3 ) 3 SiO [{CH 2 = C (CH 3 ) COO (CH 2 ) 6 } CH 3 SiO] 10 Si (CH 3 ) 3 , (CH 3 ) 3 SiO [{CH 2 = C (CH 3) COO (CH 2 ) 6} CH 3 SiO] 5 {(CH 3) 2 SiO}
10 Si (CH 3) 3, (CH 3) 3 SiO [{CH 2 = C (CH 3) COO (CH 2) 10} CH 3 SiO] 10 Si (CH 3) 3, (CH 3) 3 SiO [ {CH 2 = C (CH 3 ) COO (CH 2) 10} CH 3 SiO] 5 {(CH 3) 2 Si
O} 10 Si (CH 3) 3, (CH 3) 3 SiO [{CH 2 = CHCOO (CH 2) 6} CH 3 SiO] 10 Si (CH 3) 3, (CH 3) 3 SiO [{CH 2 = CHCOO (CH 2 ) 6 } CH 3 SiO] 5 {(CH 3 ) 2 SiO} 10 Si
(CH 3) 3, (CH 3) 3 SiO [{CH 2 = CHCOO (CH 2) 10} CH 3 SiO] 10 Si (CH 3) 3, (CH 3) 3 SiO [{CH 2 = CHCOO (CH 2 ) 10 } CH 3 SiO] 5 {(CH 3 ) 2 SiO} 10 S
i (CH 3 ) 3 ,

【００３１】[0031]

【実施例】次に、本発明の実施例をあげる。 実施例１ ジムロート冷却器、温度計、空気導入管、滴下ロートを
備えた1000mlセパラブルフラスコに、ＤＢＵ 175.1g(1.
15モル) とトルエン150.0gを仕込んだ。これを空気バブ
リング下、攪拌しながら室温でアクリル酸79.3g(1.10モ
ル) をゆっくり滴下した。この後、反応系を90℃まで加
熱した。ここへ、式Next, examples of the present invention will be described. Example 1 In a 1000 ml separable flask equipped with a Dimroth condenser, a thermometer, an air introduction tube, and a dropping funnel, 175.1 g of DBU (1.
15 mol) and 150.0 g of toluene were charged. Under air bubbling, 79.3 g (1.10 mol) of acrylic acid was slowly added dropwise at room temperature while stirring. After this, the reaction system was heated to 90 ° C. Here the formula

【化１１】 （式中、ａは平均10を示す。）で表される化合物136.5g
をゆっくり滴下した。Embedded image (In the formula, a represents 10 on average.) 136.5 g of a compound represented by
Was slowly added dropwise.

【００３２】滴下終了後、90〜100 ℃で３時間加熱攪拌
して熟成した。熟成終了後、冷却してから生成した塩を
濾別し、濾過液を80℃/5mmHgにて減圧濃縮したところ14
5.1gの濃紫色透明な液体が得られた。このものの赤外線
吸収スペクトル分析、 1Ｈ−核磁気共鳴スペクトル分析
を行ったところ、式After completion of dropping, the mixture was aged by heating and stirring at 90 to 100 ° C. for 3 hours. After the aging was completed, the resulting salt was filtered off, and the filtrate was concentrated under reduced pressure at 80 ° C / 5 mmHg.
5.1 g of a deep purple transparent liquid was obtained. Infrared absorption spectrum analysis and 1 H-nuclear magnetic resonance spectrum analysis of this product revealed that

【化１２】 （式中、ａは平均10を示す。）で表される化合物である
ことが判った。このものの収率は84.3％であった。Embedded image It was found that the compound represented by the formula (a represents an average of 10). The yield of this product was 84.3%.

【００３３】〈赤外線吸収スペクトル分析結果〉 1726cm-1：-COO- 1408 ：Si-CH3 1262 ： 〃 1191 ：SiOSi 1073 ： 〃 〈 1Ｈ−核磁気共鳴スペクトル分析結果〉 δ(ppm) 0.16(3H,s) ：≡Si-CH 3 0.93(2H,d-d) ：≡Si-CH 2-CH2 1.40〜2.03(2H,m) ：≡Si-CH2-CH 2-CH2 4.05(2H,t) ：-CH2-CH 2-O-CO- 5.56〜6.56(3H,m) ：-O-CO-CH=CH 2 <Infrared absorption spectrum analysis result> 1726 cm -1 : -COO-1408: Si-CH 3 1262: 〃 1191: SiOSi 1073: 〃 < 1 H-nuclear magnetic resonance spectrum analysis result> δ (ppm) 0.16 (3H , s): ≡Si-C H 3 0.93 (2H, dd): ≡Si-C H 2 -CH 2 1.40 to 2.03 (2H, m): ≡Si-CH 2 -C H 2 -CH 2 4.05 (2H , t): -CH 2 -C H 2 -O-CO- 5.56 ~ 6.56 (3H, m): -O-CO-C H = C H 2

【００３４】実施例２ 実施例１において、クロロプロピル基を有する環状シロ
キサンを先に滴下し、次いでアクリル酸を90℃にて滴下
した。その後は実施例１と同様に処理して139.2gの濃紫
色の液体を得た。この場合の収率は80.9％であった。Example 2 In Example 1, the cyclic siloxane having a chloropropyl group was added dropwise first, and then acrylic acid was added dropwise at 90 ° C. Thereafter, the same treatment as in Example 1 was carried out to obtain 139.2 g of a deep purple liquid. The yield in this case was 80.9%.

【００３５】実施例３ 実施例１におけるクロロプロピル基を有する環状シロキ
サンの代わりに、式{Cl(CH2)3}(CH3)2SiO{(CH3)2SiO}10
Si(CH3)2{(CH2)3Cl}で表される化合物513.5gとした他
は、実施例１と同様に処理して453.4gの濃紫色透明な液
体を得た。このものの赤外線吸収スペクトル分析、 1Ｈ
−核磁気共鳴スペクトル分析を行ったところ、式{CH2=C
HCOO(CH2)3}(CH3)2SiO{(CH3)2SiO}10Si(CH3)2{(CH2)3OO
CCH=CH2}で表される化合物であることが判った。このも
のの収率は81.5％であった。Example 3 Instead of the cyclic siloxane having a chloropropyl group in Example 1, the formula {Cl (CH 2 ) 3 } (CH 3 ) 2 SiO {(CH 3 ) 2 SiO} 10 was used.
The same process as in Example 1 was carried out except that 513.5 g of a compound represented by Si (CH 3 ) 2 {(CH 2 ) 3 Cl} was used to obtain 453.4 g of a deep purple transparent liquid. Infrared absorption spectrum analysis of this product, 1 H
− When nuclear magnetic resonance spectrum analysis was performed, the formula {CH 2 = C
HCOO (CH 2) 3} ( CH 3) 2 SiO {(CH 3) 2 SiO} 10 Si (CH 3) 2 {(CH 2) 3 OO
It was found to be a compound represented by CCH = CH 2 }. The yield of this product was 81.5%.

【００３６】実施例４ 実施例１におけるクロロプロピル基を有する環状シロキ
サンの代わりに、式(CH3)3SiO{(CH3)2SiO}7[{Cl(CH2)3}
CH3SiO]3Si(CH3)3で表される化合物363.2gとした他は実
施例１と同様に処理して、344.9gの濃紫色透明な液体を
得た。このものの赤外線吸収スペクトル分析、 1Ｈ−核
磁気共鳴スペクトル分析を行ったところ、式(CH3)3SiO
{(CH3)2SiO}7[{CH2=CHCOO(CH2)3}CH3SiO]3Si(CH3)3 で
表される化合物であることが判った。このものの収率は
86.5％であった。Example 4 Instead of the cyclic siloxane having a chloropropyl group in Example 1, the formula (CH 3 ) 3 SiO {(CH 3 ) 2 SiO} 7 [{Cl (CH 2 ) 3 }.
The same treatment as in Example 1 was carried out except that 363.2 g of a compound represented by CH 3 SiO] 3 Si (CH 3 ) 3 was used to obtain 344.9 g of a deep purple transparent liquid. Infrared absorption spectrum analysis and 1 H-nuclear magnetic resonance spectrum analysis of this product revealed that it had the formula (CH 3 ) 3 SiO
It was found to be a compound represented by {(CH 3 ) 2 SiO} 7 [{CH 2 = CHCOO (CH 2 ) 3 } CH 3 SiO] 3 Si (CH 3 ) 3 . The yield of this product is
It was 86.5%.

【００３７】実施例５ 実施例１においてアクリル酸に代えてメタクリル酸 94.
6gとした他は実施例１と同様に処理して157.5gの濃紫色
透明な液体を得た。このものの赤外線吸収スペクトル分
析、 1Ｈ−核磁気共鳴スペクトル分析を行ったところ、
式Example 5 Methacrylic acid in place of acrylic acid in Example 1 94.
The same treatment as in Example 1 was carried out except that the amount was changed to 6 g to obtain 157.5 g of a deep purple transparent liquid. Infrared absorption spectrum analysis and 1 H-nuclear magnetic resonance spectrum analysis of this product revealed that
formula

【化１３】 で表される化合物であることが判った。このものの収率
は84.7％であった。Embedded image It was found to be a compound represented by. The yield of this product was 84.7%.

【００３８】比較例１ 実施例１におけるＤＢＵの代りにトリエチルアミン116.
2g（1.15モル）とし、さらに加熱攪拌時間を15時間とし
た他は、実施例１と同様にして128.5gの褐色透明な液体
を得た。しかしながら、 1Ｈ−核磁気共鳴スペクトル分
析の結果、アクリル官能基は30％が導入されたのみであ
ることが確認された。Comparative Example 1 Instead of DBU in Example 1, triethylamine 116.
128.5 g of a brown transparent liquid was obtained in the same manner as in Example 1 except that the amount was 2 g (1.15 mol), and the heating and stirring time was 15 hours. However, as a result of 1 H-nuclear magnetic resonance spectrum analysis, it was confirmed that only 30% of the acrylic functional group was introduced.

【００３９】比較例２ 実施例１におけるＤＢＵの代りにピリジン 90.9g（1.15
モル）とし、加熱攪拌時間を15時間とした他は、実施例
１と同様にして134.2gの褐色透明な液体を得た。しかし
ながら、 1Ｈ−核磁気共鳴スペクトル分析の結果、アク
リル官能基は50％が導入されたのみであることが確認さ
れた。Comparative Example 2 90.9 g (1.15 g) of pyridine was used instead of DBU in Example 1.
Mol) and the heating and stirring time was 15 hours, and 134.2 g of a brown transparent liquid was obtained in the same manner as in Example 1. However, as a result of 1 H-nuclear magnetic resonance spectrum analysis, it was confirmed that only 50% of the acrylic functional group was introduced.

【００４０】[0040]

【発明の効果】本発明により、（メタ）アクリル官能基
含有シロキサンを容易にかつ安価に製造することのでき
る新規な方法が提供された。本発明ではＤＢＵをハロゲ
ン化水素捕捉剤として用いるが、これにより80℃〜100
℃という低温で反応を完結させることができる。また、
生成するＤＢＵ塩が大径の粗粒状となるので濾別が極め
て容易であり従来法に比較して作業性に優れている。さ
らに、使用したＤＢＵはほぼ定量的に回収できるのでコ
ストも低く抑えることができる。Industrial Applicability According to the present invention, there is provided a novel method by which a (meth) acrylic functional group-containing siloxane can be easily and inexpensively produced. In the present invention, DBU is used as a hydrogen halide scavenger.
The reaction can be completed at a low temperature of ° C. Also,
Since the DBU salt produced becomes coarse particles with a large diameter, filtration is extremely easy and workability is superior to conventional methods. Further, since the used DBU can be collected almost quantitatively, the cost can be kept low.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】（ａ）（メタ）アクリル酸（Ｉ） CH2=CR1-COOH ・・・（Ｉ） （式中、R1はメチル基または水素原子を示す。）と
（ｂ）平均組成式（II） (XR2)k(CH3)m(R3)nSiO(4-k-m-n)/2 ・・・（II） （式中、Ｘはハロゲンを示し、R2は炭素数１以上の２価
炭化水素基を示し、R3は炭素数１以上の１価有機基を示
し、ｋ＋ｍ＋ｎ≦４、０＜ｋ≦４、０≦ｍ＜４、０≦ｎ
＜４である。）で表されるハロアルキル官能性有機けい
素化合物とを（ｃ）１，８−ジアザビシクロ［５．４．
０］ウンデセン−７の存在下に反応させることを特徴と
する、平均組成式 (III) (CH2=CR1-COOR2)k(CH3)m(R3)nSiO(4-k-m-n)/2 ・・・(III) （式中、R1はメチル基または水素原子を示し、R2は炭素
数１以上の２価炭化水素基を示し、R3は炭素数１以上の
１価有機基を示し、ｋ＋ｍ＋ｎ≦４、０＜ｋ≦４、０≦
ｍ＜４、０≦ｎ＜４である。）で表される（メタ）アク
リル官能基含有有機けい素化合物の製造方法。1. (a) (Meth) acrylic acid (I) CH 2 = CR 1 -COOH (I) (wherein R 1 represents a methyl group or a hydrogen atom) and (b) average. Compositional formula (II) (XR 2 ) k (CH 3 ) m (R 3 ) n SiO (4-kmn) / 2 (II) (In the formula, X represents halogen and R 2 has 1 carbon atom. The above divalent hydrocarbon group is shown, R 3 is a monovalent organic group having 1 or more carbon atoms, k + m + n ≦ 4, 0 <k ≦ 4, 0 ≦ m <4, 0 ≦ n
<4. ) And a haloalkyl-functional organosilicon compound represented by the formula (c) 1,8-diazabicyclo [5.4.
[0] Undecene-7 in the presence of an average compositional formula (III) (CH 2 = CR 1 -COOR 2 ) k (CH 3 ) m (R 3 ) n SiO (4-kmn) / 2 ··· (III) (wherein, R 1 represents a methyl group or a hydrogen atom, R 2 represents one or more divalent hydrocarbon group having a carbon number, R 3 is a monovalent organic one or more carbon atoms A group, k + m + n ≦ 4, 0 <k ≦ 4, 0 ≦
m <4 and 0 ≦ n <4. ) A method for producing a (meth) acrylic functional group-containing organosilicon compound represented by
JP7370693A 1993-03-31 1993-03-31 Method for producing (meth) acrylic functional group-containing organosilicon compound Expired - Fee Related JP2688469B2 (en)

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JP2688469B2 true JP2688469B2 (en) 1997-12-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7105693B2 (en) 2003-01-09 2006-09-12 Shin-Etsu Chemical Co., Ltd. Process for production of alkoxysilane-based compound

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7350253B2 (en) * 2019-07-23 2023-09-26 長瀬産業株式会社 Bishaloalkylsiloxane compound and method for producing the same, and method for producing a siloxane compound having both terminal functionalities

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高分子論文集，５０〜２！ （１９９３），１２７−１３０．

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7105693B2 (en) 2003-01-09 2006-09-12 Shin-Etsu Chemical Co., Ltd. Process for production of alkoxysilane-based compound

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