JP6191566B2 - Organosilicon compound - Google Patents
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- OUSUSVATBNECFE-GLIMQPGKSA-N C/C=C(/ON)\O[N](O)(O)O[N](O)(O)O/C(/ON)=C\C Chemical compound C/C=C(/ON)\O[N](O)(O)O[N](O)(O)O/C(/ON)=C\C OUSUSVATBNECFE-GLIMQPGKSA-N 0.000 description 1
Description
本発明は、新規有機ケイ素化合物に関するものであり、特にアルコキシシリル化剤、硬化剤、表面処理剤、鎖長延長剤、アルコールスカベンジャーなどとしての保存安定剤等として有用な新規有機ケイ素化合物に関する。 The present invention relates to a novel organosilicon compound, and more particularly to a novel organosilicon compound useful as a storage stabilizer as an alkoxysilylating agent, a curing agent, a surface treating agent, a chain extender, an alcohol scavenger and the like.
α，ω−ジヒドロキシポリジメチルシロキサン等のオルガノポリシロキサンの末端アルコキシシリル化剤としては、種々のアルコキシシラン類が公知である。例えば、テトラメトキシシラン、メチルトリメトキシシラン、テトラエトキシシラン等のシラン類が挙げられ、さらに特許文献１や特許文献２には高活性なアルコキシシリル化剤が開示されている。
しかしながら、従来公知のアルコキシシリル化剤は、反応性等において未だ満足すべきものでなく、さらに反応性等の特性が向上したアルコキシシリル化剤が望まれていた。
Various alkoxysilanes are known as terminal alkoxysilylating agents for organopolysiloxanes such as α, ω-dihydroxypolydimethylsiloxane. For example, silanes such as tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane and the like can be mentioned, and Patent Document 1 and Patent Document 2 disclose highly active alkoxysilylating agents.
However, conventionally known alkoxysilylating agents are still unsatisfactory in reactivity and the like, and an alkoxysilylating agent having improved properties such as reactivity has been desired.
従って、本発明の目的は、オルガノポリシロキサンの末端アルコキシシリル化剤や硬化剤等の用途に有用な新規有機ケイ素化合物を提供することにある。 Accordingly, an object of the present invention is to provide a novel organosilicon compound useful for applications such as terminal alkoxysilylating agents and curing agents for organopolysiloxanes.
本発明者らは、上記目的を達成するために鋭意研究した結果、アクリル酸エステル類とハイドロジェン（アルコキシ）シロキサン化合物とをヒドロシリル化反応させて得られる化合物、特に、下記式（１）で示されるジケテンシリルアセタール型化合物が、反応性等の特性が向上したアルコキシシリル化剤として有用であることを見出し、本発明をなすに至った。 As a result of diligent research to achieve the above object, the present inventors have shown that a compound obtained by subjecting an acrylic ester and a hydrogen (alkoxy) siloxane compound to a hydrosilylation reaction, particularly represented by the following formula (1): It was found that the diketene silyl acetal type compound is useful as an alkoxysilylating agent having improved properties such as reactivity, and has led to the present invention.
即ち、本発明は、下記の有機ケイ素化合物を提供するものである。
〔１〕下記式（１）
That is, the present invention provides the following organosilicon compounds.
[1] The following formula (1)
〔式中、Ｒ、Ｒ1及びＲ2は置換又は非置換の炭素原子数１〜１２の一価炭化水素基であり、同一でも異なっていてもよい。ａは０〜２の整数を示す。〕
で表されるジケテンシリルアセタール型化合物。
[Wherein, R, R 1 and R 2 are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, which may be the same or different. a shows the integer of 0-2. ]
The diketene silyl acetal type compound represented by these.
〔２〕ＲとＲ2が互いに異なるものである〔１〕記載のジケテンシリルアセタール型化合物。 [2] The diketene silyl acetal type compound according to [1], wherein R and R 2 are different from each other.
本発明の新規有機ケイ素化合物は、アルコール類、シラノール類と効率よく反応し、工業的に有用なα，ω−ジヒドロキシポリジメチルシロキサン等のオルガノポリシロキサンの末端アルコキシシリル化剤や硬化剤、あるいはシリカの表面処理剤や鎖長延長剤、アルコール等のスカベンジャーとして脱アルコールタイプＲＴＶの保存安定剤等として有用である。 The novel organosilicon compound of the present invention efficiently reacts with alcohols and silanols, and is useful for industrially useful organopolysiloxanes such as α, ω-dihydroxypolydimethylsiloxane, terminal alkoxysilylating agents and curing agents, or silica. It is useful as a storage stabilizer for dealcohol type RTV, as a surface treatment agent, a chain extender, and a scavenger for alcohol.
本発明の有機ケイ素化合物は、上記式（１）で表されるジケテンシリルアセタール型化合物である。 The organosilicon compound of the present invention is a diketene silyl acetal type compound represented by the above formula (1).
ここで、前記一般式（１）において、Ｒ、Ｒ1及びＲ2で表される炭素原子数１〜１２の一価炭化水素基は、直鎖状、環状、分岐状のいずれでもよく、例えばメチル基、エチル基、プロピル基、ｎ−ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖アルキル基、シクロヘキシル基等の環状アルキル基及びイソプロピル基、イソブチル基、ｔｅｒｔ-ブチル基、２−エチルヘキシル基等の分岐状アルキル基や、これらの基の水素原子の一部又は全部を塩素、フッ素、臭素等のハロゲン原子で置換したクロロメチル基、ブロモエチル基、トリフルオロプロピル基等のハロゲン置換一価炭化水素基等を挙げることができる。
これらの基は同一であっても異なっていてもよい。本発明において好適なＲ及びＲ1はメチル基、エチル基であり、Ｒ2は炭素原子数１〜８のアルキル基、特にメチル基、エチル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ-ブチル基、２−エチルヘキシル基が好ましい。なお、上記式（１）で表されるジケテンシリルアセタール型化合物は、分子中に加水分解速度の異なる複数種の加水分解性基（即ち、−ＯＲ基と−ＯＲ2基）を含有することができることから、ＲとＲ2については互いに異なるものであることが好ましい。
また、ａは０〜２の整数である。
Here, in the general formula (1), the monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R, R 1 and R 2 may be linear, cyclic or branched. Straight chain alkyl group such as methyl group, ethyl group, propyl group, n-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclic alkyl group such as cyclohexyl group, isopropyl group, isobutyl group, tert -Branched alkyl groups such as butyl group and 2-ethylhexyl group, and chloromethyl group, bromoethyl group, trifluoropropyl in which some or all of hydrogen atoms of these groups are substituted with halogen atoms such as chlorine, fluorine, bromine And halogen-substituted monovalent hydrocarbon groups such as a group.
These groups may be the same or different. R and R 1 preferably used in the present invention are a methyl group and an ethyl group, and R 2 is an alkyl group having 1 to 8 carbon atoms, particularly a methyl group, an ethyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. A 2-ethylhexyl group is preferred. In addition, the diketene silyl acetal type compound represented by the above formula (1) may contain a plurality of hydrolyzable groups (that is, —OR group and —OR 2 group) having different hydrolysis rates in the molecule. Since it can do, it is preferable that R and R 2 are different from each other.
Moreover, a is an integer of 0-2.
上記一般式（１）で表される本発明の有機ケイ素化合物は、そのケイ素−酸素結合が、比較的温和な条件下で開裂するケテンシリルアセタール構造を分子中に二つ有していることから、アルコール類、シラノール類と効率よく反応する。従って、この新規有機ケイ素化合物は、工業的に有用なα，ω−ジヒドロキシポリジメチルシロキサン等のオルガノポリシロキサンの末端アルコキシシリル化剤や硬化剤、あるいはシリカの表面処理剤、アルコール等のスカベンジャーとして脱アルコールタイプＲＴＶの保存安定剤等として有用である。 The organosilicon compound of the present invention represented by the general formula (1) has two ketene silyl acetal structures in the molecule whose silicon-oxygen bond is cleaved under relatively mild conditions. Reacts efficiently with alcohols and silanols. Therefore, this novel organosilicon compound can be removed as an industrially useful scavenger such as terminal alkoxysilylating agent or curing agent of organopolysiloxane such as α, ω-dihydroxypolydimethylsiloxane, surface treatment agent of silica, alcohol or the like. It is useful as a storage stabilizer for alcohol type RTV.
製造方法
本発明のジケテンシリルアセタール型化合物は、アクリル酸エステル類とハイドロジェン（アルコキシ）シロキサン化合物とを反応させることによって製造することができる。この反応式は、例えば次式［１］で表される。
Production Method The diketene silyl acetal type compound of the present invention can be produced by reacting an acrylate ester with a hydrogen (alkoxy) siloxane compound. This reaction formula is represented, for example, by the following formula [1].
〔式中、Ｒ、Ｒ１、Ｒ２及びａは前記の通りである。〕 [Wherein, R, R 1 , R 2 and a are as defined above. ]
この反応は、上記式［１］から明らかな通り、アクリル酸エステル類に対するハイドロジェン（アルコキシ）シロキサン化合物のヒドロシリル（ＳｉＨ）基の１，４−付加反応である。この場合、本発明において、ハイドロジェン（アルコキシ）シロキサン化合物としては、下記に示すものが好適に用いられる。 This reaction is a 1,4-addition reaction of a hydrosilyl (SiH) group of a hydrogen (alkoxy) siloxane compound with respect to acrylic acid esters, as is apparent from the above formula [1]. In this case, in the present invention, as the hydrogen (alkoxy) siloxane compound, those shown below are preferably used.
（式中、Ｍｅはメチル基、Ｅｔはエチル基を示す。） (In the formula, Me represents a methyl group, and Et represents an ethyl group.)
このようなハイドロジェン（アルコキシ）シロキサン化合物は、例えば、アルコキシシランを酸または塩基を触媒として加水分解することで得ることができる。 Such a hydrogen (alkoxy) siloxane compound can be obtained, for example, by hydrolyzing alkoxysilane using an acid or a base as a catalyst.
一方、上記ハイドロジェン（アルコキシ）シロキサン化合物と反応させて用いるアクリル酸エステル類としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル等が好適なものとして挙げられる。 On the other hand, preferable examples of the acrylic esters used by reacting with the hydrogen (alkoxy) siloxane compound include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like.
本発明で用いるハイドロジェン（アルコキシ）シロキサン化合物とアクリル酸エステルの量は、ハイドロジェン（アルコキシ）シロキサン化合物１モルに対してアクリル酸エステル２．０モル以上とすることが好ましい。 The amount of the hydrogen (alkoxy) siloxane compound and acrylic ester used in the present invention is preferably 2.0 mol or more per mol of the hydrogen (alkoxy) siloxane compound.
上記反応は、通常、公知の付加反応触媒の存在下で行われる。かかる触媒としては、白金族金属系触媒、例えば白金系、パラジウム系、ロジウム系のものがあるが、白金系のものが特に好適である。この白金系のものとしては、白金黒あるいはアルミナ、シリカ等の担体に固体白金を担持させたもの、塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィンとの錯体あるいは白金とビニルシロキサンとの錯体等を例示することができる。これらの触媒の使用量は、所謂触媒量でよく、例えば前記アクリル酸エステルとハイドロジェン（アルコキシ）シロキサン化合物との合計量に対して、白金族金属換算で０．１〜１０００ｐｐｍ、特に０．５〜１００ｐｐｍの量が好ましい。 The above reaction is usually performed in the presence of a known addition reaction catalyst. Such catalysts include platinum group metal catalysts such as platinum, palladium and rhodium, with platinum being particularly preferred. Examples of the platinum-based material include platinum black, alumina, silica, or the like supported on solid platinum, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefin, or platinum and vinylsiloxane. And the like can be exemplified. The amount of these catalysts used may be a so-called catalytic amount, for example, 0.1 to 1000 ppm in terms of platinum group metal, particularly 0.5 to the total amount of the acrylate ester and the hydrogen (alkoxy) siloxane compound. An amount of ˜100 ppm is preferred.
この反応は、一般に５０〜１２０℃、特に６０〜１００℃の温度で、０．５〜１２時間、特に１〜６時間行うことが望ましく、また溶媒を使用せずに行うことができるが、上記付加反応等に悪影響を与えない限りにおいて、必要によりトルエン、キシレン等の適当な溶媒を使用してもよい。 This reaction is generally preferably carried out at a temperature of 50 to 120 ° C., particularly 60 to 100 ° C., for 0.5 to 12 hours, particularly 1 to 6 hours, and can be carried out without using a solvent. As long as it does not adversely affect the addition reaction, an appropriate solvent such as toluene or xylene may be used if necessary.
さらに、上記反応において、重合禁止剤を添加してもよい。重合禁止剤としては、イルガノックス１３３０（チバ・ガイキ社製、商品名）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（チバ・ガイキ社製）等が挙げられる。重合禁止剤の添加量は、一般的な重合禁止剤を用いる際の添加量でよい。 Furthermore, a polymerization inhibitor may be added in the above reaction. Examples of the polymerization inhibitor include Irganox 1330 (manufactured by Ciba Gaiki Co., Ltd., trade name), 2,6-di-tert-butyl-4-methylphenol (Ciba Gaiki Co., Ltd.), and the like. The addition amount of the polymerization inhibitor may be the addition amount when a general polymerization inhibitor is used.
また上記式［１］の反応によれば、本発明の有機ケイ素化合物以外に、下記化学式で表される異性体が、副反応生成物として極僅か生成する。 Further, according to the reaction of the above formula [1], in addition to the organosilicon compound of the present invention, an isomer represented by the following chemical formula is generated as a side reaction product.
〔式中、Ｒ、Ｒ1、Ｒ２及びａは前記の通りである。〕 [Wherein, R, R 1 , R 2 and a are as defined above. ]
これら副反応生成物の生成量は極僅かであり、また本発明の有機ケイ素化合物の異性体であって、その特性に悪影響を与えないことから、これらを分離することなく、末端アルコキシシリル化剤、シリカの表面処理剤、保存安定剤、硬化剤等の用途に使用することができる。 The production amount of these side reaction products is very small, and is an isomer of the organosilicon compound of the present invention and does not adversely affect the properties thereof. It can be used for applications such as silica surface treatment agents, storage stabilizers, and curing agents.
以下、実施例、比較例、参考例及び比較参考例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記例において、Ｍｅはメチル基、Ｅｔはエチル基を表し、「部」は「質量部」を意味する。 EXAMPLES Hereinafter, although an Example, a comparative example, a reference example, and a comparative reference example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me represents a methyl group, Et represents an ethyl group, and “part” means “part by mass”.
［合成例１］
攪拌機、還流冷却管、温度計及び滴下ロートを備えた２Ｌのセパラブルフラスコに、トリメトキシシラン ６１０ｇ（５モル）、メタノール９０ｇを加え、氷浴下にて４℃まで冷却した。目標温度に到達したのを確認したのち、滴下ロートに純水４５ｇ（２．５モル）、濃塩酸０．１５ｇ、メタノール４５ｇの混合溶液を加え、温度が１０℃以下になるよう滴下した。１２時間常温で反応させ、ガスクロマトグラフィーにて反応終了を確認し、５０℃、２０００Ｐａの条件で蒸留精製することで１４８．６ｇ（収率３０％）の下記化合物１を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、３．６〜３．８ｐｐｍ（１２Ｈ、−ＯＣＨ３）、４．２〜４．５ｐｐｍ（２Ｈ、Ｓｉ−Ｈ）]
[Synthesis Example 1]
To a 2 L separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 610 g (5 mol) of trimethoxysilane and 90 g of methanol were added and cooled to 4 ° C. in an ice bath. After confirming that the target temperature was reached, a mixed solution of 45 g (2.5 mol) of pure water, 0.15 g of concentrated hydrochloric acid and 45 g of methanol was added to the dropping funnel, and the mixture was added dropwise so that the temperature was 10 ° C. or lower. It was made to react at normal temperature for 12 hours, the completion | finish of reaction was confirmed by gas chromatography, and 148.6 g (yield 30%) of the following compound 1 was obtained by carrying out distillation purification on 50 degreeC and 2000 Pa conditions. The synthesis was confirmed by 1 H-NMR.
[1 H-NMR, 400MHz, CDCl 3, 3.6~3.8ppm (12H, -OCH 3), 4.2~4.5ppm (2H, Si-H)]
［合成例２］
合成例１において、トリメトキシシランをトリエトキシシラン９００ｇ（５．０モル）、メタノールをエタノールに変更した以外は同様の手法で合成を行い８０℃、２０００Ｐａの条件で蒸留精製することで１５９ｇ（収率２５％）の下記化合物２を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、１．５〜１．７ｐｐｍ（１２Ｈ、−ＯＣＨ２ＣＨ３）、３．７〜３．８５ｐｐｍ（８Ｈ、−ＯＣＨ２ＣＨ３）、４．２〜４．５ｐｐｍ（２Ｈ、Ｓｉ−Ｈ）]
[Synthesis Example 2]
In Synthesis Example 1, synthesis was conducted in the same manner except that trimethoxysilane was changed to 900 g (5.0 mol) of trimethoxysilane and methanol was changed to ethanol, and 159 g (yield) was obtained by distillation and purification at 80 ° C. and 2000 Pa. The following compound 2 having a rate of 25% was obtained. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 1.5 to 1.7 ppm (12H, —OCH 2 CH 3 ), 3.7 to 3.85 ppm (8H, —OCH 2 CH 3 ), 4.2 to 4 .5 ppm (2H, Si-H)]
［合成例３］
合成例１において、トリメトキシシランをメチルジメトキシシラン５３０ｇ（５．０モル）に変更した以外は同様の手法で合成を行い４０℃、２０００Ｐａの条件で蒸留精製することで８３ｇ（収率３２％）の下記化合物３を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、０．２〜０．４ｐｐｍ（６Ｈ、Ｓｉ−ＣＨ３）、３．６〜３．８ｐｐｍ（６Ｈ、−ＯＣＨ３）、４．２〜４．５ｐｐｍ（２Ｈ、Ｓｉ−Ｈ）]
[Synthesis Example 3]
In Synthesis Example 1, except that trimethoxysilane was changed to 530 g (5.0 mol) of methyldimethoxysilane, the synthesis was performed in the same manner, and then purified by distillation under the conditions of 40 ° C. and 2000 Pa (yield 32%). The following compound 3 was obtained. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 0.2 to 0.4 ppm (6H, Si—CH 3 ), 3.6 to 3.8 ppm (6H, —OCH 3 ), 4.2 to 4.5 ppm ( 2H, Si-H)]
[実施例１］
攪拌機、還流冷却管、温度計及び滴下ロートを備えた５００ｍｌの四つ口フラスコに、合成例１で得られた化合物１を４５ｇ（０．２３モル）、塩化白金酸（Ｈ2ＰｔＣｌ6・６Ｈ2Ｏ）０．３ｇ、イルガノックス１３３０（チバ・ガイギ社製重合禁止剤）０．３ｇ、２，６−ジ−ｔ−ブチル−４−メチルフェノール（チバ・ガイギ社製重合禁止剤）０．３ｇを入れ、加熱攪拌しながら温度を５０℃に上げた。
次いで、攪拌下で、エチルアクリレート４６．０５ｇ（０．４６モル）を滴下していくと、発熱が認められ、反応温度は５０〜６０℃となり、４時間、この温度に反応系を保持した。反応終了後、１９０℃、３００Ｐａの条件で減圧蒸留することで６９．０７ｇ（収率７６％）の下記目的化合物４を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、１．１〜１．３ｐｐｍ（６Ｈ、−ＯＣＨ2ＣＨ3）、１．５〜１．６ｐｐｍ（６Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）、３．５〜３．６５ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ3）、３．６〜３．８ｐｐｍ（１２Ｈ、Ｓｉ−ＯＣＨ３）、４．０〜４．１５ｐｐｍ（２Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）]
[Example 1]
In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 45 g (0.23 mol) of Compound 1 obtained in Synthesis Example 1 and chloroplatinic acid (H 2 PtCl 6 .6H) were obtained. 2 O) 0.3 g, Irganox 1330 (polymerization inhibitor manufactured by Ciba-Gaigi) 0.3 g, 2,6-di-t-butyl-4-methylphenol (polymerization inhibitor manufactured by Ciba-Gigi) 0. 3 g was added, and the temperature was raised to 50 ° C. with heating and stirring.
Next, when 46.05 g (0.46 mol) of ethyl acrylate was added dropwise with stirring, an exotherm was observed, the reaction temperature became 50-60 ° C., and the reaction system was maintained at this temperature for 4 hours. After completion of the reaction, 69.07 g (yield 76%) of the following target compound 4 was obtained by distillation under reduced pressure at 190 ° C. and 300 Pa. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 1.1 to 1.3 ppm (6H, —OCH 2 CH 3 ), 1.5 to 1.6 ppm (6H, —O (CCHCH 3 ) O—), 5 to 3.65 ppm (4H, —OCH 2 CH 3 ), 3.6 to 3.8 ppm (12H, Si—OCH 3 ), 4.0 to 4.15 ppm (2H, —O (CCHCH 3 ) O—) ]
［実施例２］
実施例１においてエチルアクリレート４６．０５ｇをｎ−ブチルアクリレート５８．９６ｇ（０．４６モル）に変更した以外は同様の手法で合成した。反応終了後、２１０℃、３００Ｐａの条件で減圧蒸留することで６８．０６ｇ（収率６６％）の下記目的化合物５を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、０．８〜０．９ｐｐｍ（６Ｈ、−ＯＣＨ2ＣＨ2ＣＨ2ＣＨ3）、１．２〜１．３ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ2ＣＨ2ＣＨ3）、１．２〜１．３ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ2ＣＨ2ＣＨ3）、１．５〜１．６ｐｐｍ（６Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）、３．５〜３．６５ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ3）、３．６〜３．８ｐｐｍ（１２Ｈ、Ｓｉ−ＯＣＨ３）、４．０〜４．１５ｐｐｍ（２Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）]
[Example 2]
Synthesis was performed in the same manner as in Example 1 except that 46.05 g of ethyl acrylate was changed to 58.96 g (0.46 mol) of n-butyl acrylate. After completion of the reaction, 68.06 g (yield 66%) of the following target compound 5 was obtained by distillation under reduced pressure at 210 ° C. and 300 Pa. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 0.8 to 0.9 ppm (6H, —OCH 2 CH 2 CH 2 CH 3 ), 1.2 to 1.3 ppm (4H, —OCH 2 CH 2 CH 2 CH 3), 1.2~1.3ppm (4H, -OCH 2 CH 2 CH 2 CH 3), 1.5~1.6ppm (6H, -O (CCHCH 3) O -), 3.5~3. 65 ppm (4H, —OCH 2 CH 3 ), 3.6 to 3.8 ppm (12 H, Si—OCH 3 ), 4.0 to 4.15 ppm (2H, —O (CCHCH 3 ) O—)]
［実施例３］
実施例１においてエチルアクリレート４６．０５ｇを２−エチルヘキシルアクリレート８４．７６ｇ（０．４６モル）に変更した以外は同様の手法で合成した。目的化合物の蒸留精製が困難であったため、低沸点化合物を減圧留去することで７１．３４ｇ（収率６８％）の下記目的化合物６を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、０．８〜０．９ｐｐｍ（１２Ｈ、−ＯＣＨ2ＣＨ2（ＣＨ2ＣＨ３）ＣＨ2ＣＨ2ＣＨ2ＣＨ3）、１．１〜１．６ｐｐｍ（２６Ｈ、−ＯＣＨ2ＣＨ2（ＣＨ2ＣＨ３）ＣＨ2ＣＨ2ＣＨ2ＣＨ3、−Ｏ（ＣＣＨＣＨ３）Ｏ−）、３．５〜３．６５ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ3）、３．６〜３．８ｐｐｍ（１２Ｈ、Ｓｉ−ＯＣＨ３）、４．０〜４．１５ｐｐｍ（２Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）]
[Example 3]
Synthesis was performed in the same manner as in Example 1 except that 46.05 g of ethyl acrylate was changed to 84.76 g (0.46 mol) of 2-ethylhexyl acrylate. Since distillation of the target compound was difficult, 71.34 g (yield 68%) of the following target compound 6 was obtained by distilling off the low boiling point compound under reduced pressure. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 0.8 to 0.9 ppm (12H, —OCH 2 CH 2 (CH 2 CH 3 ) CH 2 CH 2 CH 2 CH 3 ), 1.1 to 1.6 ppm ( 26H, -OCH 2 CH 2 (CH 2 CH 3) CH 2 CH 2 CH 2 CH 3, -O (CCHCH 3) O -), 3.5~3.65ppm (4H, -OCH 2 CH 3), 3 .6 to 3.8 ppm (12H, Si—OCH 3 ), 4.0 to 4.15 ppm (2H, —O (CCHCH 3 ) O—)]
［実施例４］
実施例１において化合物１、４５ｇ（０．２３モル）を化合物２、５０．４２（０．２３モル）に変更した以外は同様の手法で合成した。反応終了後、２２０℃、３００Ｐａの条件で減圧蒸留することで６８．０６ｇ（収率６６％）の下記目的化合物７を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、１．１〜１．３ｐｐｍ（１８Ｈ、−ＯＣＨ2ＣＨ3、Ｓｉ−ＯＣＨ2ＣＨ3）、１．５〜１．６ｐｐｍ（６Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）、３．５〜３．６５ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ3）、３．７〜３．９ｐｐｍ（８Ｈ、Ｓｉ−ＯＣＨ2ＣＨ3）、４．０〜４．１５ｐｐｍ（２Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）]
[Example 4]
Synthesis was performed in the same manner as in Example 1, except that Compound 1, 45 g (0.23 mol) was changed to Compound 2, 50.42 (0.23 mol). After completion of the reaction, 68.06 g (yield 66%) of the following target compound 7 was obtained by distillation under reduced pressure at 220 ° C. and 300 Pa. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 1.1 to 1.3 ppm (18H, —OCH 2 CH 3 , Si—OCH 2 CH 3 ), 1.5 to 1.6 ppm (6H, —O (CCHCH 3 ) O -), 3.5~3.65ppm (4H , -OCH 2 CH 3), 3.7~3.9ppm (8H, Si-OCH 2 CH 3), 4.0~4.15ppm (2H, -O (CCHCH 3) O-)]
［実施例５］
実施例１において化合物１、４５ｇ（０．２３モル）を化合物３、３８．２５（０．２３モル）に変更した以外と同様の手法で合成した。反応終了後、１７０℃、３００Ｐａの条件で減圧蒸留することで６０．７０ｇ（収率７２％）の下記目的化合物８を得た。合成確認は１Ｈ−ＮＭＲにて行った。
[１Ｈ−ＮＭＲ、４００ＭＨｚ、ＣＤＣｌ３、０．２〜０．４ｐｐｍ（６Ｈ、Ｓｉ−ＣＨ３）、１．１〜１．３ｐｐｍ（６Ｈ、−ＯＣＨ2ＣＨ3）、１．５〜１．６ｐｐｍ（６Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）、３．５〜３．６５ｐｐｍ（４Ｈ、−ＯＣＨ2ＣＨ3）、３．６〜３．８ｐｐｍ（６Ｈ、Ｓｉ−ＯＣＨ３）、４．０〜４．１５ｐｐｍ（２Ｈ、−Ｏ（ＣＣＨＣＨ３）Ｏ−）]
[Example 5]
The compound was synthesized in the same manner as in Example 1, except that Compound 1, 45 g (0.23 mol) was changed to Compound 3, 38.25 (0.23 mol). After completion of the reaction, 60.70 g (yield 72%) of the following target compound 8 was obtained by distillation under reduced pressure at 170 ° C. and 300 Pa. The synthesis was confirmed by 1 H-NMR.
[ 1 H-NMR, 400 MHz, CDCl 3 , 0.2 to 0.4 ppm (6H, Si—CH 3 ), 1.1 to 1.3 ppm (6H, —OCH 2 CH 3 ), 1.5 to 1. 6 ppm (6H, —O (CCHCH 3 ) O—), 3.5 to 3.65 ppm (4H, —OCH 2 CH 3 ), 3.6 to 3.8 ppm (6H, Si—OCH 3 ), 4.0 ~4.15ppm (2H, -O (CCHCH 3 ) O-)]
［参考例１］
粘度２００００ｍＰａ・ｓの分子鎖両末端が水酸基で封鎖されたジメチルポリシロキサン１００部と化合物４を５部、テトラメチルグアニジルプロピルトリメトキシシランを０．６部加え、湿気遮断下で均一になるまで混合して組成物を調製した。
[Reference Example 1]
Add 100 parts of dimethylpolysiloxane with both ends of the molecular chain having a viscosity of 20000 mPa · s blocked with hydroxyl groups, 5 parts of compound 4 and 0.6 part of tetramethylguanidylpropyltrimethoxysilane, and uniform under moisture blocking To prepare a composition.
［参考例２］
参考例１において、化合物４の代わりに、化合物５を５部用いた以外は同様に組成物を調製した。
[Reference Example 2]
A composition was prepared in the same manner as in Reference Example 1 except that 5 parts of Compound 5 was used instead of Compound 4.
［参考例３］
参考例１において、化合物４の代わりに、化合物６を５部用いた以外は同様に組成物を調製した。
[Reference Example 3]
A composition was prepared in the same manner as in Reference Example 1 except that 5 parts of Compound 6 was used instead of Compound 4.
［参考例４］
参考例１において、化合物４の代わりに、化合物７を５部用いた以外は同様に組成物を調製した。
[Reference Example 4]
A composition was prepared in the same manner as in Reference Example 1 except that 5 parts of Compound 7 was used instead of Compound 4.
［参考例５］
参考例１において、化合物４の代わりに、化合物８を５部用いた以外は同様に組成物を調製した。
[Reference Example 5]
A composition was prepared in the same manner as in Reference Example 1 except that 5 parts of Compound 8 was used instead of Compound 4.
［比較参考例１］
参考例１において、化合物４の代わりに、ビニルトリメトキシシラン５部を用いた以外は同様に組成物を調製した。
[Comparative Reference Example 1]
In Reference Example 1, a composition was prepared in the same manner except that 5 parts of vinyltrimethoxysilane was used instead of compound 4.
［比較参考例２］
参考例１において、化合物４の代わりに、化合物９（下記式９）５部を用いた以外は同様に組成物を調製した。
[Comparative Reference Example 2]
In Reference Example 1, a composition was prepared in the same manner except that 5 parts of Compound 9 (Formula 9) was used instead of Compound 4.
［比較参考例３］
参考例１において、化合物４の代わりに、化合物１０（下記式１０）５部を用いた以外は同様に組成物を調製した。
[Comparative Reference Example 3]
In Reference Example 1, a composition was prepared in the same manner except that 5 parts of Compound 10 (Formula 10 below) was used instead of Compound 4.
試験例
次に、各参考例及び比較参考例で調製された調製直後の各組成物を厚さ２ｍｍのシート状に押し出し、２３℃，５０％ＲＨの空気に曝し、次いで、該シートを同じ雰囲気下に７日間放置して得た硬化物の物性を、ＪＩＳ Ｋ−６２４９に準拠して測定した。なお、硬さは、ＪＩＳ Ｋ−６２４９のデュロメーターＡ硬度計を用いて測定した。
指触乾燥時間（タックフリータイム）はアルコール洗浄した中指でシリコーン組成物を指触し、付着がなくなる時間とした。
また、内径が２８ｍｍ、深さが１５ｍｍのガラス製容器に各組成物を充填し、２３℃，５０％ＲＨの空気に曝し、２４時間経過後、空気に触れた部分から硬化していく厚さを測定した（硬化膜厚）。
Test Example Next, each composition just prepared in each Reference Example and Comparative Reference Example was extruded into a sheet having a thickness of 2 mm, exposed to air at 23 ° C. and 50% RH, and then the sheet was subjected to the same atmosphere. The physical properties of the cured product obtained by allowing to stand for 7 days were measured according to JIS K-6249. In addition, hardness was measured using the durometer A hardness meter of JIS K-6249.
The touch-drying time (tack-free time) was defined as the time when the silicone composition was touched with the alcohol-washed middle finger and no adhesion occurred.
Also, each glass composition having an inner diameter of 28 mm and a depth of 15 mm is filled with each composition and exposed to air at 23 ° C. and 50% RH. Was measured (cured film thickness).
表１に参考例１〜５及び比較参考例１〜３の結果を示す。 Table 1 shows the results of Reference Examples 1 to 5 and Comparative Reference Examples 1 to 3.
以上のように、本発明の有機ケイ素化合物（ジケテンシリルアセタール型化合物）は、α，ω−ジヒドロキシポリジメチルシロキサン等のオルガノポリシロキサンの硬化剤として優れていることが分かる。 As described above, it can be seen that the organosilicon compound of the present invention (diketene silyl acetal type compound) is excellent as a curing agent for organopolysiloxanes such as α, ω-dihydroxypolydimethylsiloxane.
Claims (2)
〔式中、Ｒ、Ｒ１及びＲ２は置換又は非置換の炭素原子数１〜１２の一価炭化水素基であり、同一でも異なっていてもよい。ａは１又は２を示す。〕
で表されるジケテンシリルアセタール型化合物からなるアルコキシシリル化剤。 Following formula (1)
[Wherein, R, R 1 and R 2 are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, which may be the same or different. a represents 1 or 2 . ]
An alkoxysilylating agent comprising a diketene silyl acetal type compound represented by the formula:
The alkoxysilylating agent comprising a diketene silyl acetal type compound according to claim 1, wherein R and R 2 are different from each other.
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