JPH11322938A - Liquid solventless silicone resin and its preparation - Google Patents
Liquid solventless silicone resin and its preparationInfo
- Publication number
- JPH11322938A JPH11322938A JP15541198A JP15541198A JPH11322938A JP H11322938 A JPH11322938 A JP H11322938A JP 15541198 A JP15541198 A JP 15541198A JP 15541198 A JP15541198 A JP 15541198A JP H11322938 A JPH11322938 A JP H11322938A
- Authority
- JP
- Japan
- Prior art keywords
- silicone resin
- group
- represented
- liquid
- vinyl
- 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.)
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- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一種の液状無溶剤
シリコン樹脂とその製法に関し、該樹脂はポリ三有機基
シロキサン（Ａ）と、不飽和炭化水素基の有機シクロシ
ロキサン（Ｂ）と、ジフェニルジヒドロキシシラン
（Ｃ）を一定比率で混合後、陰イオン重合触媒の存在下
で、平衡縮合重合反応を進行して得られるもので、本発
明の液状無溶剤シリコン樹脂は無色透明であり、保存
上、安定性があり、各種の補強剤を採用して補強しうる
ものとされている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid solvent-free silicone resin and a method for producing the same, wherein the resin comprises a poly (triorganic) siloxane (A), an unsaturated hydrocarbon-containing organocyclosiloxane (B), It is obtained by mixing diphenyldihydroxysilane (C) at a fixed ratio and then proceeding with an equilibrium condensation polymerization reaction in the presence of an anionic polymerization catalyst. The liquid solventless silicone resin of the present invention is colorless and transparent, In addition, it is stable and can be reinforced by using various reinforcing agents.
【０００２】[0002]
【従来の技術】周知のとおり、シリコン樹脂は多官能基
の有機クロロシラン或いは有機アルコキシシランなどを
加水分解縮合重合反応せしめることにより製造され、加
熱或いは触媒の存在下では、さらなる変化により三次元
ネットワーク構造の不溶不溶融の熱硬化性産物が得ら
れ、硬化後のシリコン樹脂は良好な絶縁性を有し、広
い、温度、湿度及び周波数範囲で安定しており、さらに
良好な抗酸化、耐アーク、耐放射、耐気候、防水、防
塩、防カビなどの特性を有する。このためシリコン樹脂
を基材として、絶縁ワニス、塗料、成形材料など各種の
製品が生産されており、各工業部門で広く応用されてい
る。2. Description of the Related Art As is well known, a silicone resin is produced by subjecting a polyfunctional organic chlorosilane or an organic alkoxysilane to a hydrolysis-condensation polymerization reaction, and in a heating or in the presence of a catalyst, a three-dimensional network structure is formed by a further change. An insoluble and insoluble thermosetting product is obtained, and the cured silicone resin has good insulation properties, is stable over a wide temperature, humidity and frequency range, and has better anti-oxidation, arc resistance, It has properties such as radiation resistance, climate resistance, waterproofing, saltproofing, and moldproofing. For this reason, various products such as insulating varnishes, paints, molding materials and the like are produced using silicon resin as a base material, and are widely applied in various industrial sectors.
【０００３】ほとんどのシリコン樹脂は、縮合型硬化方
式橋かけ結合で三次元ネットワーク構造をなす。このよ
うな樹脂中には多くのシラノール（ｓｉｌａｎｏｌ）が
含まれており、ガラス繊維、石英粉などの無機フィラー
を添加した後に、成形材料として用いられうるが、ただ
し加圧成形時には低分子化合物を放出して気泡を発生す
ることがあり、且つ透明の製品を製造することはできな
かった。[0003] Most silicone resins form a three-dimensional network structure by condensation-curing crosslinking. Such a resin contains a large amount of silanol, and can be used as a molding material after adding an inorganic filler such as glass fiber or quartz powder. It could release air bubbles to produce a transparent product.
【０００４】ジメチルジクロロシラン（ｄｉｍｅｔｈｙ
ｌ ｄｉｃｈｌｏｒｏ ｓｉｌａｎｅ，（ＣＨ3 ）2 Ｓ
ｉＣｌ2 ）、ジフェニルジクロロシラン（ｄｉｐｈｅｎ
ｙｌｄｉｃｈｌｏｒｏ ｓｉｌａｎｅ，（Ｃ6 Ｈ5 ）2
ＳｉＣｌ2 ）、フェニルトリクロロシラン（ｐｈｅｎｙ
ｌ ｔｒｉｃｈｌｏｒｏ ｓｉｌａｎｅ，（Ｃ6 Ｈ 5 ）
2 ＳｉＣｌ3 ）及びビニルメチルジクロロシラン（ＣＨ
2 ＝ＣＨ−Ｓｉ ＣＨ2 Ｃｌ2 ）を原料とし、加水分解
縮合反応の後、製造される樹脂のシラノール含有量は極
めて少なく、ビニル基を含む重合型シリコン樹脂を加熱
し及び過酸化物を開始剤として用いて、ビニル基二重結
合を開いて重合して形成した三次元ネットワーク構造を
有する産物は、加圧成形する時に低分子物を放出しない
が、ただし樹脂硬化時の収縮率が比較的大きく、応力開
裂の現象を発生しやすかった。[0004] Dimethyldichlorosilane (dimethy)
l dichloro silane, (CHThree)TwoS
iClTwo), Diphenyldichlorosilane (diphen)
yldichloro silane, (C6HFive)Two
SiClTwo), Phenyltrichlorosilane (pheny)
l trichlorosilane, (C6H Five)
TwoSiClThree) And vinylmethyldichlorosilane (CH
Two= CH-Si CHTwoClTwo) As raw material and hydrolysis
After the condensation reaction, the silanol content of the resin produced is extremely low.
Heats polymerized silicone resin containing vinyl groups
And a peroxide as an initiator to form a vinyl group double bond.
Open a three-dimensional network structure
Products that do not release low molecular weight materials when pressed
However, the shrinkage ratio during resin curing is relatively large,
Cracking phenomenon was easy to occur.
【０００５】[0005]
【発明が解決しようとする課題】本発明は一種の液状無
溶剤シリコン樹脂とその製法を提供することを課題と
し、本発明の液状無溶剤シリコン樹脂は、上述の従来の
シリコン樹脂の有する欠点を解決し、重合型硬化方式を
採用しても、成形して硬化させる方式を採用しても、比
較的良好な強度を有し、収縮率が小さく、裂け目を発生
しない。SUMMARY OF THE INVENTION An object of the present invention is to provide a kind of liquid solventless silicone resin and a method for producing the same. The liquid solventless silicone resin of the present invention has the above-mentioned disadvantages of the conventional silicone resin. Even if a polymerization-type curing method or a molding and curing method is adopted, the resin composition has relatively good strength, a small shrinkage rate, and does not generate a crack.
【０００６】[0006]
【課題を解決するための手段】請求項１の発明は、以下
のＡからＣで示される材料、即ち、 Ａ．上記化学構造式１に示されるジメチルポリシロキサ
ン（ｄｉｍｅｔｈｙｌｐｏｌｙ ｓｉｌｏｘａｎｅ）に
おいて、上記化学構造式１中、Ｒ1 はメチル基又はビニ
ル基、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 はメチル基、ビニル基、
或いはフェニル基の有機基、ｍとｎは０〜１０００とさ
れるもの、 Ｂ．上記化学構造式２で示されるビニルメチルシクロシ
ロキサン（ｖｉｎｙｌｍｅｔｈｙｌ ｃｙｃｌｏ）にお
いて、上記化学構造式２中、Ｒ6 とＲ7 はメチル基、ビ
ニル基或いはフェニル基とされ、望ましくはＲ6 はメチ
ル基或いはフェニル基とされ、Ｒ7 はビニル基とされ、
ｐは３、４或いは５とされるもの、 Ｃ．以下の化学構造式３で示されるジフェニルジヒドロ
キシシラン（ｄｉｐｈｅｎｙｌ ｄｉｈｙｄｒｏｘｙ
ｓｉｌａｎｅ）、以上を一定比率で混合して陰イオン重
合触媒の存在下で、１４０〜１８０℃で反応を進行させ
て液状無溶剤シリコン樹脂を得る、液状無溶剤シリコン
樹脂の製法としている。According to the first aspect of the present invention, there is provided a material represented by the following A to C: In the dimethylpolysiloxane represented by Chemical Formula 1, in Chemical Formula 1, R 1 is a methyl group or a vinyl group, R 2 , R 3 , R 4 , and R 5 are a methyl group or a vinyl group. ,
Or an organic group of a phenyl group, wherein m and n are 0 to 1000; In the vinylmethylcyclosiloxane represented by Chemical Formula 2, in Chemical Formula 2, R 6 and R 7 are a methyl group, a vinyl group, or a phenyl group, and preferably, R 6 is a methyl group or A phenyl group, R 7 is a vinyl group,
p is 3, 4 or 5; A diphenyldihydroxysilane represented by the following chemical structural formula 3
The above method is a method for producing a liquid solventless silicone resin by mixing the above at a fixed ratio and advancing the reaction at 140 to 180 ° C. in the presence of an anion polymerization catalyst to obtain a liquid solventless silicone resin.
【０００７】請求項２の発明は、上記反応を、１５０〜
１６０℃で進行させる、請求項１に記載の液状無溶剤シ
リコン樹脂の製法としている。[0007] The invention according to claim 2 is the above-mentioned reaction,
The method is a method for producing a liquid solventless silicone resin according to claim 1, wherein the process is carried out at 160 ° C.
【０００８】請求項３の発明は、上記Ａ、Ｂ、Ｃで示さ
れる材料のモル比が、１〜５：１：５〜１となるように
することを特徴とする、請求項１に記載の液状無溶剤シ
リコン樹脂の製法としている。According to a third aspect of the present invention, the molar ratio of the materials represented by A, B, and C is set to 1-5: 1: 5-1. Liquid non-solvent silicone resin.
【０００９】請求項４の発明は、上記陰イオン重合触媒
を、ＫＨＯ、ＬｉＨＯ或いはそれに類するアルカリ金属
水酸化物を含むグループから一つを選択するか、或いは
それらとシクロシロキサンの反応生成物である珪酸カリ
ウム（ｐｏｔａｓｓｉｕｍｓｉｌａｎｅ）、珪酸ナトリ
ウム（ｓｏｄｉｕｍ ｓｉｌａｎｅ）、珪酸リチウム
（ｌｉｔｈｉｕｍ ｓｉｌａｎｅ）或いはそれに類する
ものとなすことを特徴とする、請求項１に記載の液状無
溶剤シリコン樹脂の製法としている。According to a fourth aspect of the present invention, the anionic polymerization catalyst is selected from the group containing KHO, LiHO or an alkali metal hydroxide similar thereto, or is a reaction product of these with cyclosiloxane. 2. The method for producing a liquid solvent-free silicone resin according to claim 1, wherein the silicate is potassium silicate, sodium silicate, lithium silicate, or the like.
【００１０】請求項５の発明は、上記陰イオン重合触媒
の重量を、上記Ａ、Ｂ、Ｃで示される材料の重量の総和
の０．００５〜０．０４％（アルカリ金属水酸化物重量
計による）となすことを特徴とする、請求項１に記載の
液状無溶剤シリコン樹脂の製法としている。According to a fifth aspect of the present invention, the weight of the anionic polymerization catalyst is 0.005 to 0.04% of the total weight of the materials represented by A, B, and C (the weight of the alkali metal hydroxide). ). The method for producing a liquid solvent-free silicone resin according to claim 1, wherein
【００１１】請求項６の発明は、上記反応に減圧縮重合
反応系を採用し、その真空度は０．０１ＭＰａ〜０．０
９５ＭＰａとすることを特徴とする、請求項１に記載の
液状無溶剤シリコン樹脂の製法としている。The invention according to claim 6 employs a reduced-compression polymerization reaction system in the above reaction, and the degree of vacuum is 0.01 MPa to 0.0 MPa.
The method according to claim 1, wherein the pressure is 95 MPa.
【００１２】請求項７の発明は、請求項１から請求項６
のいずれかに記載の液状無溶剤シリコン樹脂の製法によ
り得られる液状無溶剤シリコン樹脂としている。The invention according to claim 7 is the invention according to claims 1 to 6.
And a liquid solvent-free silicone resin obtained by the method for producing a liquid solvent-free silicone resin described in any one of the above.
【００１３】[0013]
【発明の実施の形態】本発明の液状無溶剤シリコン樹脂
は、以下のＡからＣのもの、即ち、 Ａ．上記の化学構造式１に示されるジメチルポリシロキ
サン（ｄｉｍｅｔｈｙｌ ｐｏｌｙ ｓｉｌｏｘａｎ
ｅ）において、上記化学構造式１中、Ｒ1 はメチル基又
はビニル基、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5はメチル基、ビニ
ル基、或いはフェニル基の同じ或いは異なる有機基、望
ましくはメチル基とされ、ｍとｎは０〜１０００とされ
るもの、 Ｂ．上記化学構造式２で示されるビニルメチルシクロシ
ロキサン（ｖｉｎｙｌｍｅｔｈｙｌ ｃｙｃｌｏ）にお
いて、上記化学構造式２中、Ｒ6 とＲ7 はメチル基、ビ
ニル基或いはフェニル基とされ、望ましくはＲ6 はメチ
ル基或いはフェニル基とされ、Ｒ7 はビニル基とされ、
ｐは３、４或いは５とされて、その中、最も望ましくは
４とされるもの、 Ｃ．上記化学構造式３で示されるジフェニルジヒドロキ
シシラン（ｄｉｐｈｅｎｙｌ ｄｉｈｙｄｒｏｘｙ ｓ
ｉｌａｎｅ）。上述のＡ、Ｂ、Ｃはそれぞれ周知の有機
シリコン常用原料とされ、いずれも商品として提供され
ており、これらを一定の比率で陰イオン重合触媒の存在
下で反応させて、本発明の液状無溶剤シリコン樹脂を得
る。こうして得られた本発明の液状無溶剤シリコン樹脂
は過去の文献にはなく、周知のものではない。BEST MODE FOR CARRYING OUT THE INVENTION The liquid solvent-free silicone resin of the present invention has the following A to C, namely: Dimethyl polysiloxane represented by the above chemical structural formula 1
In e), in Chemical Formula 1, R 1 is a methyl group or a vinyl group, and R 2 , R 3 , R 4 , and R 5 are the same or different organic groups of a methyl group, a vinyl group, or a phenyl group, preferably A methyl group, m and n being from 0 to 1000, B. In the vinylmethylcyclosiloxane represented by Chemical Formula 2, in Chemical Formula 2, R 6 and R 7 are a methyl group, a vinyl group, or a phenyl group, and preferably, R 6 is a methyl group or A phenyl group, R 7 is a vinyl group,
p is 3, 4 or 5, of which p is most preferably 4. The diphenyldihydroxysilane represented by the above chemical structural formula 3
ilan)). The above-mentioned A, B, and C are each a well-known organic silicon common raw material, all of which are provided as commercial products. Obtain solvent silicone resin. The thus obtained liquid solventless silicone resin of the present invention is not described in the past literature and is not well known.
【００１４】本発明では、上述のＡ、Ｂ、Ｃで示される
材料を一定の比率に分けた後、モル計算により、各グル
ープの用量が、１〜１．５：１：５〜１のモル比となる
ようにする。そして、陰イオン重合触媒の存在作用下
で、材料に平衡縮重合反応を進行させ、即ち、陰イオン
重合触媒存在作用下で、材料に縮重合反応を進行させる
と同時に、Ｓｉ−Ｏ−Ｓｉ鎖の分子転位反応を発生さ
せ、分子転位基本構造が完成した後に、平衡ステップに
到達するようにし、こうして平衡縮重合反応を完成させ
る。In the present invention, after dividing the materials represented by A, B, and C into predetermined ratios, the dose of each group is calculated to be 1 to 1.5: 1: 5 to 1 by mole calculation. Ratio. Then, under the presence of the anionic polymerization catalyst, the material undergoes an equilibrium polycondensation reaction, that is, under the presence of the anion polymerization catalyst, the material undergoes the condensation polymerization reaction, and at the same time, the Si—O—Si chain After the molecular rearrangement basic structure is completed, the equilibrium step is reached, thus completing the equilibrium polycondensation reaction.
【００１５】縮重合に用いる陰イオン重合触媒はアルカ
リ金属水酸化物、例えばＫＨＯ、ＮａＯＨ、ＬｉＨＯ及
びそれとシクロシロキサンの反応産物、例えば、珪酸カ
リウム（ｐｏｔａｓｓｉｕｍ ｓｉｌａｎｅ）、珪酸ナ
トリウム（ｓｏｄｉｕｍ ｓｉｌａｎｅ）、珪酸リチウ
ム（ｌｉｔｈｉｕｍ ｓｉｌａｎｅ）とされ、その中、
望ましくは、珪酸カリウムとされ、その用量は、シリコ
ン樹脂量の０．００５〜０．０４重量％（ＫＯＨで計
算）とされ、望ましくは０．０１〜０．０２重量％とさ
れ、縮重合反応温度は１４０〜１８０℃、望ましくは１
５０〜１６０℃とされ、反応は真空下で進行され、真空
度は０．０１ＭＰａ〜０．０９５ＭＰａとされ、反応時
間は一般に１〜３時間の範囲内とされる。The anionic polymerization catalyst used for the condensation polymerization is an alkali metal hydroxide such as KHO, NaOH, LiHO and a reaction product thereof with cyclosiloxane, such as potassium silicate, sodium silicate, lithium silicate. (Lithium silane), in which
Preferably, it is potassium silicate, and its dose is 0.005 to 0.04% by weight (calculated by KOH), preferably 0.01 to 0.02% by weight of the silicone resin. The temperature is 140-180 ° C, preferably 1
The reaction is carried out under vacuum, the degree of vacuum is from 0.01 MPa to 0.095 MPa, and the reaction time is generally in the range of from 1 to 3 hours.
【００１６】本発明の液状無溶剤シリコン樹脂は、各種
補強剤を採用することで補強可能であり、補強剤を選択
する時には、その屈折指数と液状無溶剤シリコン樹脂の
マッチングを考慮する必要があり、常用される補強剤と
しては、気相法ホワイトカーボン（ｗｈｉｔｅ−ｃａｒ
ｂｏｎ）、沈殿法ホワイトカーボン、ＭＱ樹脂（ビニル
基を含むシリコン樹脂）が挙げられるが、望ましくは表
面処理を採用した疎水性気相法ホワイトカーボンｔｏｓ
ａｒｅ、補強剤の添加量は液状無溶剤シリコン樹脂の重
量の５０〜１２０％、望ましくは８０〜１００％とされ
る。The liquid solvent-free silicone resin of the present invention can be reinforced by employing various reinforcing agents. When selecting a reinforcing agent, it is necessary to consider the matching between the refractive index and the liquid solvent-free silicone resin. As a commonly used reinforcing agent, gas-phase white carbon (white-car) is used.
bon), precipitation method white carbon, and MQ resin (silicon resin containing a vinyl group), and preferably, hydrophobic gas phase method white carbon tos employing surface treatment.
are and the amount of the reinforcing agent to be added are 50 to 120%, preferably 80 to 100% of the weight of the liquid solventless silicone resin.
【００１７】[0017]
【実施例】実施例１ 攪拌器、温度計、油水分離器及び冷却器を具えた２５０
ｍｌの三つ口フラスコ内に、５９．２グラムの粘度５０
０ｃｐのトリメチルシラン（ｔｒｉｍｅｔｈｙｌ ｓｉ
ｌａｎｅ）端封のポリジメチルシロキサン（ｐｏｌｙ
ｄｉｍｅｔｈｙｌ ｓｉｌｏｘａｎｅ）、３４．４グラ
ムの１．３．５．７−テトラビニル−１．３．５．７−
テトラメチル−シクロテトラシロキサン（１．３．５．
７−ｔｅｔｒａ ｖｉｎｙｌ−１．３．５．７−ｔｅｔ
ｒａ ｍｅｔｈｙｌ−ｃｙｃｌｏｔｅｔｒａ ｓｉｌｏ
ｘａｎｅ）、２１．６グラムのジフェニルジヒドロキシ
シラン（ｄｉｐｅｎｙｌ ｄｉｈｙｄｒｏｘｙ ｓｉｌ
ａｎｅ）及び２．３グラムのジフェニルヒドロキシシラ
ンカリウム触媒（ＫＨＯの珪酸カリウム内の含有量が１
％）、以上を入れて、拡販して徐々に１５０〜１６０℃
まで加熱し、減圧を開始し、適時に反応誘導体内の脱出
した水分を除去する。１〜２時間の後、材料が透明とな
れば、すでに水分が無く、その他の低分子物は蒸発した
ことを示すので、反応を停止させれば、無色で粘りけの
ある透明なシリコン樹脂が得られる。EXAMPLE 1 250 equipped with stirrer, thermometer, oil-water separator and cooler
59.2 grams of viscosity 50 in a 3 ml three-necked flask.
0 cp of trimethylsilane
lane edge-sealed polydimethylsiloxane (poly)
dimethyl siloxane), 34.4 grams of 1.3.5.7-tetravinyl-1.3.5.7-
Tetramethyl-cyclotetrasiloxane (1.3.5.
7-tetra vinyl-1.3.5.7-tet
ra methyl-cyclotetra silo
xane), 21.6 grams of diphenyldihydroxysilane
an) and 2.3 grams of potassium diphenylhydroxysilane catalyst (KHO having a content in potassium silicate of 1).
%), Add the above, expand sales and gradually increase to 150-160 ° C
Until the pressure is reduced, and the escaped water in the reaction derivative is removed in a timely manner. After 1-2 hours, when the material becomes transparent, it indicates that there is no water and other low molecular weight substances have evaporated, so if the reaction is stopped, a colorless and sticky transparent silicone resin is obtained. Can be
【００１８】実施例２ 上述のようにして得られた無色で粘りけのある透明なシ
リコン樹脂１０グラム内に、５グラムのフェニル基含水
素シリコーンオイル、１０グラムの疎水性気相法及び微
量プラチナ触媒を加え、混練して均一となした後に１３
０℃で５分間、型内で加圧し型製品を得る。得られた型
製品は２００℃で４時間加熱しても、黄変、裂け目を発
生せず、良好な硬度、強度、透明度を有する。Example 2 In 10 grams of the colorless, viscous and transparent silicone resin obtained as described above, 5 grams of a hydrogen-containing silicone oil containing phenyl groups, 10 grams of a hydrophobic gas phase method and a trace platinum catalyst were used. And knead to make uniform
Press in the mold at 0 ° C. for 5 minutes to obtain a mold product. The obtained molded product does not cause yellowing or cracking even when heated at 200 ° C. for 4 hours, and has good hardness, strength and transparency.
【００１９】[0019]
【発明の効果】本発明は一種の液状無溶剤シリコン樹脂
とその製法を提供しており、本発明の液状無溶剤シリコ
ン樹脂は、上述の従来のシリコン樹脂の有する欠点を解
決し、重合型硬化方式を採用しても、成形して硬化させ
る方式を採用しても、比較的良好な強度を有し、収縮率
が小さく、裂け目を発生しない。According to the present invention, there is provided a kind of liquid solvent-free silicone resin and a method for producing the same. The liquid solvent-free silicone resin of the present invention solves the above-mentioned disadvantages of the conventional silicone resin, and can be cured by polymerization. Regardless of the method used or the method of molding and curing, it has a relatively good strength, a small shrinkage rate, and no cracks.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年４月２８日[Submission date] April 28, 1999
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【化１】 上記化学構造式１中、Ｒ1 はメチル基又はビニル基、Ｒ
2 、Ｒ3 、Ｒ4 、Ｒ5 はメチル基、ビニル基、或いはフ
ェニル基の有機基、ｍとｎは０〜１０００とされるも
の、 Ｂ．以下の化学構造式２で示されるビニルメチルシクロ
シロキサン（ｖｉｎｙｌ ｍｅｔｈｙｌ ｃｙｃｌｏ）
において、Embedded image In the above chemical formula 1, R 1 is a methyl group or a vinyl group;
2 , R 3 , R 4 , and R 5 are an organic group such as a methyl group, a vinyl group, or a phenyl group; m and n are from 0 to 1000; Vinyl methyl cyclosiloxane represented by the following chemical structural formula 2
At
【化２】 上記化学構造式２中、Ｒ6 とＲ7 はメチル基、ビニル基
或いはフェニル基とされ、Ｒ6 はメチル基或いはフェニ
ル基とされ、Ｒ7 はビニル基とされ、ｐは３、４或いは
５とされるもの、 Ｃ．以下の化学構造式３で示されるジフェニルジヒドロ
キシシラン（ｄｉｐｈｅｎｙｌ ｄｉｈｙｄｒｏｘｙ
ｓｉｌａｎｅ）、Embedded image In the above chemical structural formula 2, R 6 and R 7 are a methyl group, a vinyl group or a phenyl group, R 6 is a methyl group or a phenyl group, R 7 is a vinyl group, and p is 3, 4 or 5 C. A diphenyldihydroxysilane represented by the following chemical structural formula 3
silan),
【化３】 以上を、一定比率で混合して陰イオン重合触媒の存在下
で、１４０〜１８０℃で反応を進行させて液状無溶剤シ
リコン樹脂を得る、液状無溶剤シリコン樹脂の製法。Embedded image A method for producing a liquid solventless silicone resin, in which the above are mixed at a fixed ratio and the reaction is allowed to proceed at 140 to 180 ° C in the presence of an anionic polymerization catalyst to obtain a liquid solventless silicone resin.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００６】[0006]
【課題を解決するための手段】請求項１の発明は、以下
のＡからＣで示される材料、即ち、 Ａ．上記化学構造式１に示されるジメチルポリシロキサ
ン（ｄｉｍｅｔｈｙｌｐｏｌｙ ｓｉｌｏｘａｎｅ）に
おいて、上記化学構造式１中、Ｒ1 はメチル基又はビニ
ル基、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 はメチル基、ビニル基、
或いはフェニル基の有機基、ｍとｎは０〜１０００とさ
れるもの、 Ｂ．上記化学構造式２で示されるビニルメチルシクロシ
ロキサン（ｖｉｎｙｌｍｅｔｈｙｌ ｃｙｃｌｏ）にお
いて、上記化学構造式２中、Ｒ6 とＲ7 はメチル基、ビ
ニル基或いはフェニル基とされ、Ｒ6 はメチル基或いは
フェニル基とされ、Ｒ7 はビニル基とされ、ｐは３、４
或いは５とされるもの、 Ｃ．上記化学構造式３で示されるジフェニルジヒドロキ
シシラン（ｄｉｐｈｅｎｙｌ ｄｉｈｙｄｒｏｘｙ ｓ
ｉｌａｎｅ）、以上を一定比率で混合して陰イオン重合
触媒の存在下で、１４０〜１８０℃で反応を進行させて
液状無溶剤シリコン樹脂を得る、液状無溶剤シリコン樹
脂の製法としている。According to the first aspect of the present invention, there is provided a material represented by the following A to C: In the dimethylpolysiloxane represented by Chemical Formula 1, in Chemical Formula 1, R 1 is a methyl group or a vinyl group, R 2 , R 3 , R 4 , and R 5 are a methyl group or a vinyl group. ,
Or an organic group of a phenyl group, wherein m and n are 0 to 1000; In the vinylmethylcyclosiloxane represented by the chemical structural formula 2, in the chemical structural formula 2, R 6 and R 7 are a methyl group, a vinyl group or a phenyl group, and R 6 is a methyl group or a phenyl group. R 7 is a vinyl group, and p is 3, 4
Or 5; C. The diphenyldihydroxysilane represented by the above chemical structural formula 3
ilane) and a mixture of the above at a fixed ratio and in the presence of an anionic polymerization catalyst, the reaction is allowed to proceed at 140 to 180 ° C. to obtain a liquid solventless silicone resin.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００７】請求項２の発明は、上記反応を、１５０〜
１６０℃で進行させる、請求項１に記載の液状無溶剤シ
リコン樹脂の製法としている。[0007] The invention according to claim 2 is the above-mentioned reaction,
The method is a method for producing a liquid solventless silicone resin according to claim 1, wherein the process is carried out at 160 ° C.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００８】請求項３の発明は、上記Ａ、Ｂ、Ｃで示さ
れる材料のモル比が、１〜５：１：５〜１となるように
することを特徴とする、請求項１に記載の液状無溶剤シ
リコン樹脂の製法としている。According to a third aspect of the present invention, the molar ratio of the materials represented by A, B, and C is set to 1-5: 1: 5-1. Liquid non-solvent silicone resin.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】請求項４の発明は、上記陰イオン重合触媒
を、ＫＯＨ、ＬｉＯＨ或いはそれに代替可能なアルカリ
金属水酸化物を含むグループから一つを選択するか、或
いはそれらとシクロシロキサンの反応生成物である珪酸
カリウム（ｐｏｔａｓｓｉｕｍ ｓｉｌａｎｅ）、珪酸
ナトリウム（ｓｏｄｉｕｍ ｓｉｌａｎｅ）、珪酸リチ
ウム（ｌｉｔｈｉｕｍ ｓｉｌａｎｅ）或いはそれに代
替可能なものとなすことを特徴とする、請求項１に記載
の液状無溶剤シリコン樹脂の製法としている。The invention according to claim 4 is that the anion polymerization catalyst is selected from the group consisting of KOH, LiOH or an alkali metal hydroxide which can be substituted for it, or a reaction product of them with cyclosiloxane. The method for producing a liquid solventless silicone resin according to claim 1, wherein potassium silicate (sodium silicate), lithium silicate (lithium silane), or a substitute thereof is used. I have.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１０】請求項５の発明は、上記陰イオン重合触媒
の重量を、上記Ａ、Ｂ、Ｃで示される材料の重量の総和
の０．００５〜０．０４％（アルカリ金属水酸化物重量
計による）となすことを特徴とする、請求項１に記載の
液状無溶剤シリコン樹脂の製法としている。According to a fifth aspect of the present invention, the weight of the anionic polymerization catalyst is 0.005 to 0.04% of the total weight of the materials represented by A, B, and C (the weight of the alkali metal hydroxide). ). The method for producing a liquid solvent-free silicone resin according to claim 1, wherein
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】請求項６の発明は、上記反応に減圧縮重合
反応系を採用し、その真空度は０．０１ＭＰａ〜０．０
９５ＭＰａとすることを特徴とする、請求項１に記載の
液状無溶剤シリコン樹脂の製法としている。The invention according to claim 6 employs a reduced-compression polymerization reaction system in the above reaction, and the degree of vacuum is 0.01 MPa to 0.0 MPa.
The method according to claim 1, wherein the pressure is 95 MPa.
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１２】本発明は、上述の請求項１から請求項６に
記載の製法により液状無溶剤シリコン樹脂を得る。According to the present invention, a liquid solventless silicone resin is obtained by the above-described method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 蔡 吉龍 台湾台北縣淡水鎮沙崙路181巷13號７樓 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsai Jilyu, No. 13, 181 Street, Shalun Road, Tamsui Town, Taipei County, Taiwan
Claims (7)
サン（ｄｉｍｅｔｈｙｌ ｐｏｌｙ ｓｉｌｏｘａｎ
ｅ）において、 【化１】 上記化学構造式１中、Ｒ1 はメチル基又はビニル基、Ｒ
2 、Ｒ3 、Ｒ4 、Ｒ5 はメチル基、ビニル基、或いはフ
ェニル基の有機基、ｍとｎは０〜１０００とされるも
の、 Ｂ．以下の化学構造式２で示されるビニルメチルシクロ
シロキサン（ｖｉｎｙｌ ｍｅｔｈｙｌ ｃｙｃｌｏ）
において、 【化２】 上記化学構造式２中、Ｒ6 とＲ7 はメチル基、ビニル基
或いはフェニル基とされ、望ましくはＲ6 はメチル基或
いはフェニル基とされ、Ｒ7 はビニル基とされ、ｐは
３、４或いは５とされるもの、 Ｃ．以下の化学構造式３で示されるジフェニルジヒドロ
キシシラン（ｄｉｐｈｅｎｙｌ ｄｉｈｙｄｒｏｘｙ
ｓｉｌａｎｅ）、 【化３】 以上を、一定比率で混合して陰イオン重合触媒の存在下
で、１４０〜１８０℃で反応を進行させて液状無溶剤シ
リコン樹脂を得る、液状無溶剤シリコン樹脂の製法。1. The following materials A to C: Dimethyl polysiloxane represented by the following chemical structural formula 1
In e), In the above chemical formula 1, R 1 is a methyl group or a vinyl group;
2 , R 3 , R 4 , and R 5 are an organic group such as a methyl group, a vinyl group, or a phenyl group; m and n are from 0 to 1000; Vinyl methyl cyclosiloxane represented by the following chemical structural formula 2
In the formula, In the above chemical structural formula 2, R 6 and R 7 are a methyl group, a vinyl group or a phenyl group, preferably R 6 is a methyl group or a phenyl group, R 7 is a vinyl group, and p is 3, 4 Or 5; C. A diphenyldihydroxysilane represented by the following chemical structural formula 3
silane), embedded image A method for producing a liquid solventless silicone resin, in which the above are mixed at a fixed ratio and the reaction is allowed to proceed at 140 to 180 ° C in the presence of an anionic polymerization catalyst to obtain a liquid solventless silicone resin.
せる、請求項１に記載の液状無溶剤シリコン樹脂の製
法。2. The method for producing a liquid solventless silicone resin according to claim 1, wherein the reaction is allowed to proceed at 150 to 160 ° C.
が、１〜５：１：５〜１となるようにすることを特徴と
する、請求項１に記載の液状無溶剤シリコン樹脂の製
法。3. The liquid solventless silicon according to claim 1, wherein the molar ratio of the materials represented by A, B, and C is 1-5: 1: 5-1. Resin manufacturing method.
ＨＯ或いはそれに類するアルカリ金属水酸化物を含むグ
ループから一つを選択するか、或いはそれらとシクロシ
ロキサンの反応生成物である珪酸カリウム（ｐｏｔａｓ
ｓｉｕｍ ｓｉｌａｎｅ）、珪酸ナトリウム（ｓｏｄｉ
ｕｍ ｓｉｌａｎｅ）、珪酸リチウム（ｌｉｔｈｉｕｍ
ｓｉｌａｎｅ）或いはそれに類するものとなすことを
特徴とする、請求項１に記載の液状無溶剤シリコン樹脂
の製法。4. The method according to claim 1, wherein the anionic polymerization catalyst is KHO, Li
Select one from the group containing HO or similar alkali metal hydroxides, or potassium silicate (potas
sium silane, sodium silicate (sodi)
um silane, lithium silicate (lithium)
The method for producing a liquid solvent-free silicone resin according to claim 1, characterized in that the silicone resin or the like is used.
Ａ、Ｂ、Ｃで示される材料の重量の総和の０．００５〜
０．０４％（アルカリ金属水酸化物重量計による）とな
すことを特徴とする、請求項１に記載の液状無溶剤シリ
コン樹脂の製法。5. The weight of the anionic polymerization catalyst is 0.005 to 0.005 of the total weight of the materials represented by A, B and C.
The method for producing a liquid solvent-free silicone resin according to claim 1, wherein the content is 0.04% (by an alkali metal hydroxide weight meter).
その真空度は０．０１ＭＰａ〜０．０９５ＭＰａとする
ことを特徴とする、請求項１に記載の液状無溶剤シリコ
ン樹脂の製法。6. A reduced-compression polymerization reaction system is adopted in the above reaction,
The method according to claim 1, wherein the degree of vacuum is 0.01 MPa to 0.095 MPa.
の液状無溶剤シリコン樹脂の製法により得られる液状無
溶剤シリコン樹脂。7. A liquid solvent-free silicone resin obtained by the method for producing a liquid solvent-free silicone resin according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15541198A JP2950812B1 (en) | 1998-05-21 | 1998-05-21 | Liquid solvent-free silicone resin and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15541198A JP2950812B1 (en) | 1998-05-21 | 1998-05-21 | Liquid solvent-free silicone resin and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2950812B1 JP2950812B1 (en) | 1999-09-20 |
| JPH11322938A true JPH11322938A (en) | 1999-11-26 |
Family
ID=15605412
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15541198A Expired - Fee Related JP2950812B1 (en) | 1998-05-21 | 1998-05-21 | Liquid solvent-free silicone resin and its manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP2950812B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589378A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Vinyl phenyl polysiloxane and preparation method thereof |
| CN114672172A (en) * | 2022-04-28 | 2022-06-28 | 东莞市品晟有机硅科技有限公司 | Silicone rubber capable of being stored for long time by adding platinum vulcanizing agent and preparation method thereof |
-
1998
- 1998-05-21 JP JP15541198A patent/JP2950812B1/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589378A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Vinyl phenyl polysiloxane and preparation method thereof |
| CN114672172A (en) * | 2022-04-28 | 2022-06-28 | 东莞市品晟有机硅科技有限公司 | Silicone rubber capable of being stored for long time by adding platinum vulcanizing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2950812B1 (en) | 1999-09-20 |
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