JPH0348196B2 - - Google Patents
Info
- Publication number
- JPH0348196B2 JPH0348196B2 JP1665887A JP1665887A JPH0348196B2 JP H0348196 B2 JPH0348196 B2 JP H0348196B2 JP 1665887 A JP1665887 A JP 1665887A JP 1665887 A JP1665887 A JP 1665887A JP H0348196 B2 JPH0348196 B2 JP H0348196B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- stirring
- nmr
- component
- 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.)
- Expired
Links
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- LTCNUXKYERAHFO-UHFFFAOYSA-N [hydroxy(dimethyl)silyl]methyl prop-2-enoate Chemical compound C[Si](C)(O)COC(=O)C=C LTCNUXKYERAHFO-UHFFFAOYSA-N 0.000 description 5
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- ZVNDTYVBGPWWFX-UHFFFAOYSA-N methyl(prop-1-en-2-yloxy)silane Chemical compound C[SiH2]OC(C)=C ZVNDTYVBGPWWFX-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000004819 silanols Chemical class 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- HYWZOETUAIBWEZ-UHFFFAOYSA-N 3-[hydroxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O HYWZOETUAIBWEZ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization 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
- 125000005372 silanol group Chemical group 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Description
（産業上の利用分野）
本発明は文献末載の新規な有機けい素化合物、
特には光重合性のアクリルオキシオルガノシリル
基を含有することから紫外線硬化型シリコーンゴ
ム組成物用として有用される新規な有機けい素化
合物に関するものである。
（発明の構成）
本発明にかかわる有機けい素化合物は一般式
で示され、こゝにR1は水素原子またはメチル基、
R2はメチレン基、エチレン基、プロピレン基、
ブチレン基などの式（−CH2）−（式中、ｍは１〜５
の整数）で示される基、R3、R4はメチル基、エ
チル基、プロピル基、ブチル基などのアルキル
基、フエニル基、トリル基などのアリール基、ま
たはこれらの基の炭素原子に結合した水素原子の
一部または全部をハロゲン原子、で置換したクロ
ロメチル基、トリフルオロプロピル基、などから
選択される同一または異種の非置換またはハロゲ
ン置換の低級アルキル基またはアリール基、ｎは
１〜1000の整数である。
本発明の有機けい素化合物としては例えば以下
のようなものがある。
（こゝにｎ、n′は１〜1000までの整数）
前記した一般式(1)で示される本発明の有機けい
素化合物は、例えばつぎのようにして得ることが
できる一般式
（こゝにR3、R4、ｎは前記に同じ）で示される
分子鎖両末端がヒドロキシ基（OH基）で封鎖さ
れたヒドロキジオルガノポリシロキサンと、この
ヒドロキシジオルガノポリシロキサンのシラノー
ル基と当モル量の一般式
で示されるジヒドロイソプロペノキシシランとを
混合し、これらを０〜50℃、好ましくは20〜50℃
の温度で反応させて一般式
で示される分子鎖両末端がジヒドロ基で封鎖され
たジヒドロジオルガノポリシロキサンを生成さ
せ、ついでこのジヒドロジオルガノポリシロキサ
ンに前記ジヒドロイソプロペノキシシランと等モ
ル量の一般式
（こゝにR1、R2、R3、R4は前記に同じ）で示さ
れるアクリル系置換シラノールをアクリル系置換
シラノールに対して0.01〜0.1モル％、好ましく
は0.02〜0.03モル％のジエチルヒドロキシアミン
を触媒として加えて20〜80℃、好ましくは40〜60
℃の温度が脱水素反応させることによつて得るこ
とができる。
なお、前記の一般式(2)で示されるヒドロキシジ
オルガノポリシロキサンとしては
(Industrial Application Field) The present invention relates to a novel organosilicon compound described in the literature,
In particular, the present invention relates to a novel organosilicon compound that contains a photopolymerizable acryloxyorganosilyl group and is therefore useful for use in ultraviolet-curable silicone rubber compositions. (Structure of the invention) The organosilicon compound according to the present invention has the general formula , where R 1 is a hydrogen atom or a methyl group,
R 2 is a methylene group, an ethylene group, a propylene group,
Formula ( -CH2 )-(in the formula, m is 1 to 5) such as butylene group
R 3 and R 4 are an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, an aryl group such as a phenyl group or tolyl group, or a group bonded to a carbon atom of these groups. the same or different unsubstituted or halogen-substituted lower alkyl group or aryl group selected from chloromethyl groups, trifluoropropyl groups, etc. in which some or all of the hydrogen atoms are substituted with halogen atoms, n is 1 to 1000 is an integer. Examples of the organosilicon compounds of the present invention include the following. (Here, n and n' are integers from 1 to 1000.) The organosilicon compound of the present invention represented by the general formula (1) described above can be obtained, for example, by the general formula (Here, R 3 , R 4 , and n are the same as above) A hydroxydiorganopolysiloxane in which both ends of the molecular chain are blocked with hydroxy groups (OH groups) and a silanol group of this hydroxydiorganopolysiloxane General formula for equimolar amount dihydroisopropenoxysilane shown in
The general formula is obtained by reacting at a temperature of A dihydrodiorganopolysiloxane in which both ends of the molecular chain are capped with dihydro groups is produced, and then an equimolar amount of the dihydroisopropenoxysilane of the general formula (Here, R 1 , R 2 , R 3 , and R 4 are the same as above.) 0.01 to 0.1 mol%, preferably 0.02 to 0.03 mol% of diethyl substituted silanol is added to the acrylic substituted silanol. 20-80℃, preferably 40-60℃ with addition of hydroxyamine as a catalyst
℃ temperature can be obtained by dehydrogenation reaction. In addition, as the hydroxydiorganopolysiloxane represented by the above general formula (2),
【式】【formula】
【式】【formula】
などが例示され、前記した一般式(5)で示されるア
クリル系置換シラノールとしては
などが例示されるが、これらを適宜組み合わせて
反応させることによつて、前記例示したような本
発明の有機けい素化合物が合成される。
このようにして得られた本発明の有機けい素化
合物は文献末載の新規な化合物であり、アクリル
系の光重合用に市販されているアセトフエノン、
ベンゾフエノン、４，4′−ジメトキシアセトフエ
ノン、ベンゾイルブチルエーテルのような光重合
反応開始剤を本発明の有機けい素化合物に添加す
ると紫外線または電子線照射することによつて容
易にゴム状弾性体となるので、シリコーンゴム組
成物製造用原料として特に有用である。また、本
発明の有機けい素化合物のうちこの低重合度のも
のは光重合性組成物の反応性希釈剤としても有用
とされる。
つぎに本発明の実施例をあげる。
実施例 １
還流冷却器、温度計および滴下ロートを取り付
けた50mlの三ツ口フラスコにジフエニルシランジ
オール5.4ｇを仕込み、電磁撹拌しながらこのフ
ラスコにメチルイソプロペノキシシラン5.6ｇを
10分間で滴下したところ、フラスコ内温度は20℃
から40℃に上昇し、ジフエニルシランジオールは
反応して液状となつた。滴下終了後も２時間撹拌
を続けて反応を完了させたのち、ジエチルヒドロ
アミン0.05ｇを添加したところ気体が発生して脱
水素反応が始まつた。電磁撹拌をしながらこの混
合物中にアクリロキシメチルジメチルシラノール
17.6ｇを１時間で滴下したところ、滴下開始時か
ら水素が発生し、滴下終了後は50℃でさらに４時
間撹拌を続けて反応を終了させた。ついでフラス
コ中の揮発成分を減圧留去したところ、屈折率
1.4770（25℃）の物性を有する成分23.6ｇが得ら
れた。
得られた成分についてNMR、IRおよび元素分
析を行なつたところ、この成分は式
で示されるものであることが確認された。
NMR、IRおよび元素分析の結果を以下に示
す。
〔NMR〕
δ0.08 （Ｓ、 Examples of the acrylic substituted silanol represented by the general formula (5) include The organosilicon compound of the present invention as exemplified above can be synthesized by appropriately combining and reacting these. The organosilicon compound of the present invention thus obtained is a novel compound described in the literature, and includes acetophenone, which is commercially available for photopolymerization of acrylics,
When a photopolymerization initiator such as benzophenone, 4,4'-dimethoxyacetophenone, or benzoyl butyl ether is added to the organosilicon compound of the present invention, it can be easily converted into a rubber-like elastic material by irradiation with ultraviolet rays or electron beams. Therefore, it is particularly useful as a raw material for producing silicone rubber compositions. Furthermore, among the organosilicon compounds of the present invention, those having a low degree of polymerization are said to be useful as reactive diluents for photopolymerizable compositions. Next, examples of the present invention will be given. Example 1 5.4 g of diphenylsilanediol was placed in a 50 ml three-necked flask equipped with a reflux condenser, a thermometer, and a dropping funnel, and 5.6 g of methylisopropenoxysilane was added to the flask with magnetic stirring.
When added dropwise for 10 minutes, the temperature inside the flask was 20℃.
The temperature rose to 40°C, and diphenylsilanediol reacted and became liquid. After the completion of the dropwise addition, stirring was continued for 2 hours to complete the reaction. When 0.05 g of diethylhydroamine was added, gas was generated and a dehydrogenation reaction started. Add acryloxymethyldimethylsilanol to this mixture with magnetic stirring.
When 17.6 g was added dropwise over 1 hour, hydrogen was generated from the beginning of the addition, and after the addition was completed, stirring was continued for an additional 4 hours at 50°C to complete the reaction. Then, when the volatile components in the flask were distilled off under reduced pressure, the refractive index
23.6 g of a component having physical properties of 1.4770 (at 25°C) was obtained. NMR, IR and elemental analysis were performed on the obtained component, and it was found that this component has the formula It was confirmed that the The results of NMR, IR and elemental analysis are shown below. [NMR] δ0.08 (S,
【式】24H） δ0.18 （Ｓ[Formula] 24H) δ0.18 (S
【式】6H） δ3.70 （d.SiCH2−、8H） δ5.5〜6.3 （ｍ、[Formula] 6H) δ3.70 (d.SiCH 2 −, 8H) δ5.5~6.3 (m,
Ｃ Ｈ Si
計算値（％） 48.68 6.45 20.97
実測値（％） 48.8 6.3 21.0
実施例 ２
還流冷却器、温度計および滴下ロートを取り付
けた50mlの三ツ口フラスコに平均組成式が
で示される、分子鎖両末端がヒドロキシ基で封鎖
されたヒドロキシジメチルポリシロキサン10.0ｇ
を仕込み、電磁撹拌しながらメチルイソプロペノ
キシシラン2.1ｇをで滴下したところ、フラスコ
内温度は21℃から33℃６に上昇した。滴下終了後
も２時間撹拌を続けて反応を完了させたのち、ジ
エルチルヒドロキシアミン0.05ｇをフラスコ中に
滴下したところ、気体が発生して脱水素反応が始
まつた。電磁撹拌をしながらこの混合物中にアク
リロキシメチルジメチルシラノール7.0ｇを１時
間で滴下したところ、滴下開始時から水素が発生
し、滴下終了後は50℃でさらに４時間撹拌を続け
て反応を終了させた。ついでフラスコ中の揮発成
分を減圧留去したところ、屈折率1.4208（25℃）
の物性を有する成分16.1ｇが得られた。
得られた成分についてNMRおよびIR分析を行
なつたところ、この成分は平均組成式が
で示されるものであることが確認された。
以下にこのNMRおよびIRによる分析結果を示
す。
〔NMR〕
δ0.08 （Ｓ、
C H Si Calculated value (%) 48.68 6.45 20.97 Actual value (%) 48.8 6.3 21.0 Example 2 The average composition formula is 10.0g of hydroxydimethylpolysiloxane with both ends of the molecular chain blocked with hydroxy groups
When 2.1 g of methylisopropenoxysilane was added dropwise with electromagnetic stirring, the temperature inside the flask rose from 21°C to 33°C. After the completion of the addition, stirring was continued for 2 hours to complete the reaction. When 0.05 g of diethyl hydroxyamine was added dropwise into the flask, gas was generated and a dehydrogenation reaction began. When 7.0 g of acryloxymethyldimethylsilanol was dropped into this mixture over 1 hour with magnetic stirring, hydrogen was generated from the beginning of the dropwise addition, and after the dropwise addition was completed, stirring was continued for an additional 4 hours at 50°C to complete the reaction. I let it happen. Then, when the volatile components in the flask were distilled off under reduced pressure, the refractive index was 1.4208 (25℃).
16.1 g of a component having the following physical properties was obtained. NMR and IR analysis of the obtained component revealed that the average compositional formula of this component was It was confirmed that the The results of this NMR and IR analysis are shown below. [NMR] δ0.08 (S,
【式】108H） δ0.18 （Ｓ、[Formula] 108H) δ0.18 (S,
【式】6H） δ3.76 （ｓ、SiCH2−、8H） δ5.5〜6.3 （ｍ、[Formula] 6H) δ3.76 (s, SiCH 2 −, 8H) δ5.5~6.3 (m,
【式】12H）
〔IR〕……第２図参照
実施例 ３
還流冷却器、温度計および滴下ロートおよび撹
拌棒を取り付けた200mlの四ツ口フラスコに、平
均組成式が
で示される、分子鎖両末端がヒドロキシ基で封鎖
されたヒドロキシジメチルポリシロキサン100.0
ｇを仕込み、撹拌しながらメチルイソプロペノキ
シラン1.1ｇを滴下し、滴下終了後もさらに２時
間撹拌を続けて反応を完了させたのち、ジエチル
ヒドロキシアミン0.05ｇを添加したところ、気体
が発生して脱水素反応が始まつた。さらにアクリ
ロキシメチルジメチルシラノール3.8ｇを滴下し
たところ、滴下開始時から水素が発生し、滴下終
了後は50℃でさらに４時間撹拌を続けて反応を完
了させたのち、フラスコ中の揮発成分を減圧留去
したところ、屈折率1.4055（25℃）の物性を有す
る成分102.9ｇが得られた。
得られた成分についてNMRおよびIR分析を行
なつたところ、この成分は平均組成式が、
で示されるものであることが確認された。
以下にこのNMRおよびIRによる分析結果を示
す。
〔NMR〕
δ0.08 （s.[Formula] 12H) [IR]...See Figure 2 Example 3 The average compositional formula was Hydroxydimethylpolysiloxane 100.0, with both ends of the molecular chain blocked with hydroxyl groups.
1.1 g of methylisopropenoxylan was added dropwise with stirring, and after the addition was completed, stirring was continued for another 2 hours to complete the reaction. When 0.05 g of diethylhydroxyamine was added, gas was generated. The dehydrogenation reaction has begun. Furthermore, when 3.8 g of acryloxymethyldimethylsilanol was added dropwise, hydrogen was generated from the beginning of the addition, and after the addition was completed, stirring was continued for an additional 4 hours at 50°C to complete the reaction, and then the volatile components in the flask were depressurized. When distilled off, 102.9 g of a component having a physical property of a refractive index of 1.4055 (25°C) was obtained. NMR and IR analysis of the obtained component revealed that the average compositional formula of this component was It was confirmed that the The results of this NMR and IR analysis are shown below. [NMR] δ0.08 (s.
【式】） δ0.18 （ｓ【formula】) δ0.18 (s
【式】） δ3.82 （ｓ、SiCH2−） δ5.5〜6.3 （ｍ、[Formula]) δ3.82 (s, SiCH 2 −) δ5.5~6.3 (m,
【式】）
〔IR〕……第３図参照
実施例 ４
還流冷却器、温度計および滴下ロートおよび撹
拌棒を取り付けた200mlの四ツ口フラスコに平均
組成式が
で示される、分子鎖両末端がヒドロキシ基で封鎖
されたヒドロキシジメチルジフエニルポリシロキ
サン100.0ｇを仕込み、撹拌しながらメチルイソ
プロペノキシシラン0.8ｇを滴下し、滴下終了後
もさらに２時間撹拌を続けて反応を終了させたの
ち、ジエチルヒドロキシアミン0.05ｇを添加した
ところ、気体が発生し脱水素反応が始まつた。さ
らにアクリロキシメチルジメチルシラノール2.6
ｇを滴下したところ、滴下開始時から水素が発生
し、滴下終了後は50℃で４時間撹拌を続けて反応
を完了させたのち、フラスコ中の揮発成分を減圧
留去したところ、屈折率1.4486（２℃）の物性を
有する成分102.1ｇが得られた。
得られた成分についてNMRおよびIR分析を行
なつたところ、この成分は平均組成式が
で示されるものであることが確認された。
以下にNMRおよびIRによる分析結果を示す。
〔NMR〕
δ0.08 （ｓ、[Formula]) [IR]...See Figure 3 Example 4 The average compositional formula was placed in a 200 ml four-necked flask equipped with a reflux condenser, thermometer, dropping funnel, and stirring bar. Charge 100.0 g of hydroxydimethyldiphenylpolysiloxane with both ends of the molecular chain capped with hydroxyl groups, and dropwise add 0.8 g of methylisopropenoxysilane while stirring, and continue stirring for another 2 hours after the dropwise addition is complete. After the reaction was terminated, 0.05 g of diethylhydroxyamine was added, gas was generated and a dehydrogenation reaction started. Plus acryloxymethyldimethylsilanol 2.6
When the dropwise addition of 50 g was started, hydrogen was generated from the beginning of the dropwise addition. After the dropwise addition, stirring was continued for 4 hours at 50°C to complete the reaction, and the volatile components in the flask were distilled off under reduced pressure, resulting in a refractive index of 1.4486. 102.1 g of a component having physical properties of (2° C.) was obtained. NMR and IR analysis of the obtained component revealed that the average compositional formula of this component was It was confirmed that the The results of NMR and IR analysis are shown below. [NMR] δ0.08 (s,
【式】） δ0.18 （ｓ、【formula】) δ0.18 (s,
【式】） δ3.81 （ｓ、SiCH2−） δ5.5〜6.3 （ｍ、[Formula]) δ3.81 (s, SiCH 2 −) δ5.5~6.3 (m,
【式】）
δ7.1〜7.7 （ｍ、arom。）
〔IR〕……第４図参照
実施例 ５
還流冷却器、温度計および滴下ロートを取り付
けた20mlの三ツ口フラスコに平均組成式が
で示される、分子鎖両末端がヒドロキシ基で封鎖
されたヒドロキシジメチルポリシロキサン2.0ｇ
を仕込み、電磁撹拌しながらメチルイソプロペノ
キシシラン0.44ｇを10分間で滴下したところ、フ
ラスコ内温度は20℃から32℃に上昇した。滴下終
了後も２時間撹拌を続けて反応を完了させたの
ち、ジエチルヒドロキシアミン0.01ｇをフラスコ
中に滴下したところ、気体が発生して脱水素反応
が始まつた。電磁撹拌をしながらこの混合物中に
３−メタクリロキシプロピルジメチルシラノール
2.0ｇを１時間で滴下したところ、滴下開始時か
ら水素が発生し、滴下終了後は50℃でさらに４時
間撹拌を続けて反応を終了させた。ついでフラス
コ中の揮発成分を減圧留去したことろ、屈折率
1.4268（25℃）の物性を有する成分3.5ｇが得られ
た。
得られた成分についてNMRおよびIR分析した
ところ、この成分は平均組成式が
で示されるものであることが確認された。
以下にNMRおよびIRによる分析結果を示す。
〔NMR〕
δ0.08 （ｓ、[Formula]) δ7.1~7.7 (m, arom.) [IR]...Refer to Figure 4 Example 5 The average compositional formula is 2.0g of hydroxydimethylpolysiloxane with both ends of the molecular chain blocked with hydroxy groups
When 0.44 g of methylisopropenoxysilane was added dropwise over 10 minutes with magnetic stirring, the temperature inside the flask rose from 20°C to 32°C. After completing the reaction by continuing stirring for 2 hours even after the dropwise addition was completed, 0.01 g of diethylhydroxyamine was added dropwise into the flask, gas was generated and a dehydrogenation reaction started. Add 3-methacryloxypropyldimethylsilanol to this mixture with magnetic stirring.
When 2.0 g was added dropwise over 1 hour, hydrogen was generated from the beginning of the dropwise addition, and after the dropwise addition was completed, stirring was continued for an additional 4 hours at 50°C to complete the reaction. Then, the volatile components in the flask were distilled off under reduced pressure, and the refractive index was
3.5 g of a component having physical properties of 1.4268 (25°C) was obtained. NMR and IR analysis of the obtained component revealed that the average compositional formula of this component was It was confirmed that the The results of NMR and IR analysis are shown below. [NMR] δ0.08 (s,
【式】108H） δ0.18 （ｓ、[Formula] 108H) δ0.18 (s,
【式】6H） δ2.66 （ｓ、[Formula] 6H) δ2.66 (s,
【式】12H）
δ4.08 （ｔ、Ｏ−CH2、8H）
δ5.49 （ｓ、CH2＝、4H）
δ6.03 （ｓ、CH2＝、4H）
〔IR〕……第５図参照
実施例 ６
還流冷却器、温度計および滴下ロートおよび撹
拌棒を取り付けた200mlの四ツ口フラスコに平均
組成式が
で示される、分子鎖両末端がヒドロキシ基で封鎖
されたヒドロキシ３−トリフルオロプロピルメチ
ルポリシロキサン100.0ｇを仕込み、撹拌しなが
らメチルイソプロペノキシシラン2.6ｇを滴下し、
滴下終了後もさらに２時間撹拌を続けて反応を終
了させたのち、ジエチルヒドロキシアミン0.05ｇ
を添加したところ、気体が発生して脱水素反応が
始まつた。さらにアクリロキシメチルジメチルシ
ラノール2.6ｇを滴下したところ、滴下開始時か
ら水素が発生し、滴下終了後は50℃でさらに４時
間撹拌を続けて反応を完了させたのち、フラスコ
中の揮発成分を減圧留去したところ、屈折率
1.3868（25℃）の物性を有する成分109.3ｇが得ら
れた。
得られた成分についてNMRおよびIR分析を行
なつたところ、この成分は平均組成式が
で示されるものであることが確認された。
以下にNMRおよびIRによる分析結果を示す。
〔NMR〕
δ0.10 （ｓ、[Formula] 12H) δ4.08 (t, O-CH 2 , 8H) δ5.49 (s, CH 2 =, 4H) δ6.03 (s, CH 2 =, 4H) [IR]...Figure 5 Reference Example 6 A 200 ml four-necked flask equipped with a reflux condenser, thermometer, addition funnel and stirring bar has an average compositional formula. 100.0 g of hydroxy 3-trifluoropropylmethylpolysiloxane with both ends of the molecular chain capped with hydroxyl groups was charged, and 2.6 g of methylisopropenoxysilane was added dropwise while stirring.
After the addition was completed, stirring was continued for another 2 hours to complete the reaction, and then 0.05g of diethylhydroxyamine was added.
When added, gas was generated and a dehydrogenation reaction started. Furthermore, when 2.6 g of acryloxymethyldimethylsilanol was added dropwise, hydrogen was generated from the beginning of the dropwise addition. After the dropwise addition was completed, stirring was continued for an additional 4 hours at 50°C to complete the reaction, and then the volatile components in the flask were depressurized. When distilled off, the refractive index
109.3 g of a component having physical properties of 1.3868 (at 25°C) was obtained. NMR and IR analysis of the obtained component revealed that the average compositional formula of this component was It was confirmed that the The results of NMR and IR analysis are shown below. [NMR] δ0.10 (s,
【式】） δ3.83 （ｓ、SiCH2−） δ5.5〜6.3 （ｍ、[Formula]) δ3.83 (s, SiCH 2 −) δ5.5~6.3 (m,
【式】） 〔IR〕……第６図参照【formula】) [IR]...See Figure 6
図は実施例１〜６で得られた本発明の有機けい
素化合物の赤外吸収スペクトルを示したものであ
り、第１図は実施例１、第２図は実施例２、第３
図は実施例３、第４図は実施例４、第５図は実施
例５、第６図は実施例６で得られた有機けい素化
合物の赤外吸収スペクトルを示したものである。
The figures show infrared absorption spectra of the organosilicon compounds of the present invention obtained in Examples 1 to 6.
The figure shows the infrared absorption spectra of the organosilicon compounds obtained in Example 3, FIG. 4 in Example 4, FIG. 5 in Example 5, and FIG. 6 in Example 6.
Claims (1)
CH2）−ｍ（式中、ｍは１〜５の整数）で示される
基、R3、R4は同一または異種の非置換またはハ
ロゲン置換の低級アルキル基またはアリール基、
ｎは１〜1000の整数）で示される有機けい素化合
物。 ２ R2がメチレン基またはプロピレン基である
特許請求の範囲第１項記載の有機けい素化合物。[Claims] 1. General formula [Here, R 1 is a hydrogen atom or a methyl group, R 2 is (−
a group represented by CH 2 )-m (wherein m is an integer of 1 to 5), R 3 and R 4 are the same or different unsubstituted or halogen-substituted lower alkyl group or aryl group;
n is an integer from 1 to 1000). 2. The organosilicon compound according to claim 1, wherein R 2 is a methylene group or a propylene group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1665887A JPS63185989A (en) | 1987-01-27 | 1987-01-27 | organosilicon compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1665887A JPS63185989A (en) | 1987-01-27 | 1987-01-27 | organosilicon compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63185989A JPS63185989A (en) | 1988-08-01 |
| JPH0348196B2 true JPH0348196B2 (en) | 1991-07-23 |
Family
ID=11922441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1665887A Granted JPS63185989A (en) | 1987-01-27 | 1987-01-27 | organosilicon compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63185989A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5182315A (en) * | 1990-11-19 | 1993-01-26 | Loctite Corporation | Photocurable silicone gel composition, and method of making the same |
| US5179134A (en) * | 1990-11-19 | 1993-01-12 | Loctite Corporation | Photocurable silicone composition, and method of making the same |
| ATE185157T1 (en) | 1990-11-19 | 1999-10-15 | Loctite Corp | PHOTOHARDABLE POLYSILOXANE COMPOSITION AND METHOD FOR PRODUCING |
| US5348986A (en) * | 1990-11-19 | 1994-09-20 | Loctite Corporation | Photocurable silicone composition, and method of making same |
| US5212211A (en) * | 1990-11-19 | 1993-05-18 | Loctite Corporation | Polymodal-cure silicone composition, and method of making the same |
| US6818721B2 (en) * | 2002-12-02 | 2004-11-16 | Rpo Pty Ltd. | Process for producing polysiloxanes and use of the same |
| JP5812022B2 (en) * | 2013-02-12 | 2015-11-11 | 信越化学工業株式会社 | Fluorine-containing organosiloxane and process for producing the same |
| CN111247193B (en) * | 2017-10-24 | 2022-04-12 | 信越化学工业株式会社 | Method for producing organopolysiloxane, radiation-curable organopolysiloxane composition, and release sheet |
-
1987
- 1987-01-27 JP JP1665887A patent/JPS63185989A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63185989A (en) | 1988-08-01 |
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