JPH04252228A - Silicone-containing epoxy compound and production thereof - Google Patents
Silicone-containing epoxy compound and production thereofInfo
- Publication number
- JPH04252228A JPH04252228A JP904991A JP904991A JPH04252228A JP H04252228 A JPH04252228 A JP H04252228A JP 904991 A JP904991 A JP 904991A JP 904991 A JP904991 A JP 904991A JP H04252228 A JPH04252228 A JP H04252228A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- silicone
- containing epoxy
- reaction
- epoxy compound
- 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.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 239000004593 Epoxy Substances 0.000 title claims description 21
- 229920001296 polysiloxane Polymers 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000565 sealant Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl titanate Chemical class 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、耐候性、耐熱性のすぐ
れた塗料、コーティング剤、シーリング剤、接着剤など
の原料として有用なシリコーン含有エポキシ化合物及び
その製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-containing epoxy compound useful as a raw material for paints, coating agents, sealants, adhesives, etc., which have excellent weather resistance and heat resistance, and a method for producing the same.
【0002】0002
【従来の技術】分子末端あるいは、側鎖にアルコキシシ
リル基を有するビニル系重合体は公知である(特開昭5
4−36395号公報、特開昭54−40893号公報
、特開昭54−123192号公報)。ビニル系重合体
の末端あるいは側鎖に、アルコキシシリル基を導入する
ことにより、ビニル系重合体の特徴である高光沢、耐候
性、耐変色性等のすぐれた特徴だけでなく、アルコキシ
シリル基による無機物に対する密着性の向上、さらに水
分特に大気中の水分による常温架橋で、緻密な網状構造
を形成し、耐溶剤性、耐水性、耐熱性、高い硬度、耐候
性のすぐれた重合体になることが知られている。[Prior Art] Vinyl polymers having an alkoxysilyl group at the end of the molecule or in the side chain are known (Japanese Patent Laid-Open No.
4-36395, JP 54-40893, JP 54-123192). By introducing an alkoxysilyl group to the end or side chain of a vinyl polymer, it not only has the excellent characteristics of vinyl polymers such as high gloss, weather resistance, and discoloration resistance, but also the alkoxysilyl group. It improves adhesion to inorganic materials, and forms a dense network structure through room-temperature crosslinking with moisture, especially atmospheric moisture, resulting in a polymer with excellent solvent resistance, water resistance, heat resistance, high hardness, and weather resistance. It has been known.
【0003】0003
【発明が解決しようとする課題】しかしながら、最近、
建築分野において屋外外装用として、さらに耐候性のす
ぐれた塗料原料が求められている。[Problem to be solved by the invention] However, recently,
In the construction field, there is a demand for paint raw materials with even better weather resistance for outdoor exterior use.
【0004】0004
【課題を解決するための手段】本発明者らは、下記化3
で示されるラダー型ヒドロシリコーン化合物とアリルグ
リシジルエーテルとを、VIII族白金系の触媒下で反
応させることにより得られるシリコーン含有エポキシ化
合物は塗膜性能がすぐれた硬化性組成物の原料として用
いることができることを見出し、本発明を完成した。[Means for solving the problem] The present inventors have developed the following formula 3:
A silicone-containing epoxy compound obtained by reacting a ladder-type hydrosilicone compound represented by the formula with allyl glycidyl ether in the presence of a Group VIII platinum catalyst can be used as a raw material for a curable composition with excellent coating performance. They discovered what they could do and completed the present invention.
【0005】[0005]
【化3】[Chemical 3]
【0006】即ち、本発明は、下記化4で示されるシリ
コーン含有エポキシ化合物、及び下記化5で表わされる
ラダー型ヒドロシリコーン化合物とアリルグリシジルエ
ーテルとを白金系触媒の存在下、50〜150℃で反応
させることを特徴とするシリコーン含有エポキシ化合物
の製法である。That is, the present invention provides a silicone-containing epoxy compound represented by the following chemical formula 4, a ladder-type hydrosilicone compound represented by the following chemical formula 5, and allyl glycidyl ether in the presence of a platinum catalyst at 50 to 150°C. This is a method for producing a silicone-containing epoxy compound, which is characterized by a reaction.
【0007】[0007]
【化4】[C4]
【0008】[0008]
【化5】[C5]
【0009】本発明の上記化4で示されるシリコーン含
有エポキシ化合物は、新規な物質である。本発明の上記
化4で示されるシリコーン含有エポキシ化合物、架橋基
を有するビニル系重合体、及び硬化促進触媒等を配向し
た硬化性組成物は、硬化した塗膜の耐候性、耐熱性が大
巾に向上する。本発明のシリコーン含有エポキシ化合物
の製造に用いられるヒドロシリコーン化合物は、トリク
ロロシランをジオキサン等の溶媒中で水を加えて加水分
解したのち、メタノール、エタノール等の低級アルコー
ルを加えてアルコキシ化することによって得られる。The silicone-containing epoxy compound shown in formula 4 of the present invention is a new substance. The curable composition in which the silicone-containing epoxy compound shown in formula 4 above, the vinyl polymer having a crosslinking group, the curing accelerating catalyst, etc., of the present invention are oriented, has a cured coating film that has a wide range of weather resistance and heat resistance. improve. The hydrosilicone compound used in the production of the silicone-containing epoxy compound of the present invention is obtained by hydrolyzing trichlorosilane in a solvent such as dioxane by adding water, and then alkoxylating it by adding a lower alcohol such as methanol or ethanol. can get.
【0010】本発明に用いられるラダー型ヒドロシリコ
ーン化合物を具体的に示すと下記化6の通りである。The ladder-type hydrosilicone compound used in the present invention is specifically shown in the following formula 6.
【0011】[0011]
【化6】[C6]
【0012】本発明のシリコーン含有エポキシ化合物は
、ラダー型ヒドロシリコーン化合物のSi−H基にアリ
ルグリシジルエーテルを付加することにより得られるが
、この反応において第VIII族白金系触媒を必要とす
る。第VIII族白金系触媒としては白金の単体、塩化
白金酸、アルコール変性塩化白金酸、塩化白金−オレフ
ィン錯体、アルミナ、シリカ等の担体に固体白金を担持
させたもの、ロジウム−オレフィン錯体など、コバルト
、パラジウムおよびニッケルから選ばれたVIII族の
金属化合物が有効に使用される。その使用量は、通常反
応物に対して1〜1,000ppmの量が用いられる。The silicone-containing epoxy compound of the present invention is obtained by adding allyl glycidyl ether to the Si--H group of a ladder-type hydrosilicone compound, but this reaction requires a Group VIII platinum catalyst. Group VIII platinum-based catalysts include simple platinum, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinum-olefin complexes, solid platinum supported on supports such as alumina and silica, rhodium-olefin complexes, etc. Group VIII metal compounds selected from , palladium and nickel are advantageously used. The amount used is usually 1 to 1,000 ppm based on the reactants.
【0013】このヒドロシリン化反応は、50〜150
℃の温度で反応時間は1〜5時間で達成される。反応温
度が50℃以下の場合は反応速度が遅くなり実用的でな
い。また、反応温度が150℃以上になると一部高分子
量物が生成したりゲル化反応が起るので好ましくない。
本発明において、ラダー型ヒドロシリコーン化合物とア
リルグリシジルエーテルとを反応させる時のモル比は、
目標とする反応生成物により変わるが、通常、Si−H
基1モルに対して、アリルグリシジルエーテルを0.1
〜5.0モルの範囲が好ましい。[0013] This hydrosilylation reaction
At a temperature of 0.degree. C., reaction times are achieved in 1 to 5 hours. If the reaction temperature is 50°C or less, the reaction rate becomes slow and it is not practical. Furthermore, if the reaction temperature exceeds 150° C., it is not preferable because some high molecular weight substances will be produced or a gelation reaction will occur. In the present invention, the molar ratio when the ladder-type hydrosilicone compound and allyl glycidyl ether are reacted is as follows:
Although it varies depending on the target reaction product, usually Si-H
0.1 allyl glycidyl ether per mole of group
The range of 5.0 mol is preferred.
【0014】本発明において、ラダー型ヒドロシリコー
ン化合物とアリルグリシジルエーテルの反応において、
溶媒を用いてもよい。用いられる溶媒としては、ラダー
型ヒドロシリコーン化合物とアリルグリシジルエーテル
をともに溶解する溶媒が好ましい。通常、トルエン、キ
シレン等の有機溶媒が用いられる。溶媒を使用する場合
は、反応に用いられる原料1重量部に対して0.1〜1
0重量部を用いることが好ましい。In the present invention, in the reaction between the ladder-type hydrosilicone compound and allyl glycidyl ether,
A solvent may also be used. The solvent used is preferably a solvent that dissolves both the ladder-type hydrosilicone compound and allyl glycidyl ether. Usually, organic solvents such as toluene and xylene are used. When using a solvent, 0.1 to 1 part by weight of raw materials used in the reaction.
Preferably, 0 parts by weight is used.
【0015】本発明のシリコーン含有エポキシ化合物は
、大気中に暴露されるとアルコキシシリル基が、大気中
の水分と反応して常温で網状組織を形成して硬化する。
本発明のシリコーン含有エポキシ化合物は、他の架橋基
を持つ化合物と混合して硬化させることもできる。
架橋基を持つ化合物としては、例えば、分子未満あるい
は側鎖にアルコキシシリル基を持つビニル重合体等であ
る。本発明のシリコーン含有エポキシ化合物を硬化させ
るにあたっては、硬化促進剤を使用することもできる。
用いられる硬化促進剤としては、アルキルチタン酸塩、
オクチル酸スズ、およびジブチルスズジラウレート等の
如きカルボン酸の金属塩、ジブチルアミン−2−ヘキソ
エート等の如きアミン塩ならびに他の酸性硬化促進剤お
よび塩基性硬化促進剤が有効である。これら硬化促進剤
の添加量は、該化合物に対して0.01〜10重量%使
用するのが好ましい。When the silicone-containing epoxy compound of the present invention is exposed to the atmosphere, the alkoxysilyl groups react with moisture in the atmosphere to form a network structure and harden at room temperature. The silicone-containing epoxy compound of the present invention can also be mixed with other compounds having crosslinking groups and cured. Examples of the compound having a crosslinking group include a vinyl polymer having an alkoxysilyl group in a submolecule or in a side chain. In curing the silicone-containing epoxy compound of the present invention, a curing accelerator can also be used. The curing accelerator used is alkyl titanate,
Metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate, amine salts such as dibutylamine-2-hexoate, and other acidic and basic accelerators are useful. The amount of these curing accelerators added is preferably 0.01 to 10% by weight based on the compound.
【0016】本発明のシリコーン含有エポキシ化合物は
、エポキシ硬化剤と混合することにより硬化させること
もできる。エポキシ硬化剤としては通常アミン化合物が
用いられる。本発明のシリコーン含有エポキシ化合物は
、塗料、シーリング剤、コーティング剤などの原料化合
物として有用である。The silicone-containing epoxy compound of the present invention can also be cured by mixing it with an epoxy curing agent. An amine compound is usually used as the epoxy curing agent. The silicone-containing epoxy compound of the present invention is useful as a raw material compound for paints, sealants, coating agents, and the like.
【0017】本発明のシリコーン含有エポキシ化合物は
、用途に応じて、種々の充填剤、顔料等をブレンドする
ことが可能である。充填剤、顔料としては、各種シリカ
類、炭酸カルシウム、炭酸マグネシウム、酸化チタン、
酸化鉄、ガラス繊維等種々のものが使用可能である。[0017] The silicone-containing epoxy compound of the present invention can be blended with various fillers, pigments, etc. depending on the intended use. Fillers and pigments include various silicas, calcium carbonate, magnesium carbonate, titanium oxide,
Various materials such as iron oxide and glass fiber can be used.
【0018】[0018]
【実施例】以下、実施例により本発明を説明する。[Examples] The present invention will be explained below with reference to Examples.
【0019】[0019]
【実施例1】温度計、攪拌用回転子、冷却管を取付けた
300mlの3口フラスコに、アリルグリシジルエーテ
ル41.6g(365m・mol)、塩化白金酸6水塩
の5%イソプロパノール溶液0.48g、トルエン42
gを入れ、攪拌しながら温度を85℃まで上げた。次に
下記化7に示す構造式のヒドロシリコーン化合物20g
(Si−H基243m・mol)をフラスコ内へ20分
かけて滴下した。滴下終了後85℃でさらに2時間反応
した。反応液中の溶媒及び未反応のアリルグリシジルエ
ーテルを真空蒸発で除去した。液状物が43.0g得ら
れた。生成物中の未反応のSi−H基をアルカリ分解法
で測定した結果Si−H基の反応率は73.1%であっ
た。赤外吸収スペクトル及び 1H−NMRにより解析
した結果、生成物は、前記のヒドロシリコーン化合物の
Si−H基の73.1モル%が下記化8に変換した化合
物であることを確認した。[Example 1] In a 300 ml three-necked flask equipped with a thermometer, a stirring rotor, and a cooling tube, 41.6 g (365 mmol) of allyl glycidyl ether and 0.0 g of a 5% isopropanol solution of chloroplatinic acid hexahydrate were placed. 48g, toluene 42
g was added thereto, and the temperature was raised to 85°C while stirring. Next, 20 g of a hydrosilicone compound having the structural formula shown in Chemical formula 7 below.
(Si-H group 243 mmol) was dropped into the flask over 20 minutes. After the dropwise addition was completed, the reaction was continued at 85° C. for an additional 2 hours. The solvent and unreacted allyl glycidyl ether in the reaction solution were removed by vacuum evaporation. 43.0g of liquid material was obtained. As a result of measuring unreacted Si-H groups in the product by an alkaline decomposition method, the reaction rate of Si-H groups was 73.1%. As a result of analysis by infrared absorption spectrum and 1H-NMR, it was confirmed that the product was a compound in which 73.1 mol% of the Si-H groups of the hydrosilicone compound were converted to the following formula 8.
【0020】[0020]
【化7】[C7]
【0021】[0021]
【化8】[Chemical formula 8]
【0022】[0022]
【実施例2】実施例1と同じ装置を用いて、アリルグリ
シジルエーテル30.8g(270m・mol)、塩化
白金酸6水塩の5%イソプロパノール溶液0.3g、ト
ルエン50gを入れ、攪拌しながら温度を85℃まで上
げた。次に下記化9に示す構造式を持つヒドロシリコー
ン化合物20g(Si−H270m・mol)をフラス
コ内へ20分かけて滴下した。滴下終了後85℃で2時
間反応した。反応液中の溶媒及び未反応のアリルグリシ
ジルエーテルを真空蒸発で除去した結果、34.2gの
液状生成物が得られた。実施例1と同様に構造解析した
結果、生成物は原料のヒドロシリコーン化合物のSi−
H基の58%が実施例1に示す化8に変換した化合物で
あることを確認した。[Example 2] Using the same apparatus as in Example 1, 30.8 g (270 mmol) of allyl glycidyl ether, 0.3 g of a 5% isopropanol solution of chloroplatinic acid hexahydrate, and 50 g of toluene were added, and while stirring, The temperature was raised to 85°C. Next, 20 g (270 mmol of Si-H) of a hydrosilicone compound having the structural formula shown in Chemical Formula 9 below was dropped into the flask over 20 minutes. After the dropwise addition was completed, the reaction was carried out at 85° C. for 2 hours. As a result of removing the solvent and unreacted allyl glycidyl ether in the reaction solution by vacuum evaporation, 34.2 g of a liquid product was obtained. As a result of structural analysis in the same manner as in Example 1, the product was found to be Si-
It was confirmed that 58% of the H groups were converted into the compound shown in Example 1.
【0023】[0023]
【化9】[Chemical formula 9]
【0024】[0024]
【実施例3】実施例1と同じ装置に、アリルグリシジル
エーテル74.8g(656m・mol)、塩化白金酸
6水塩の5%イソプロパノール溶液0.6g、トルエン
95gを入れ、攪拌しながら温度を80℃まで上げた。
下記化10に示す構造式を持つヒドロシリコーン化合物
20g(Si−H基328m・mol)をフラスコ内へ
20分かけて滴下した。滴下終了後80℃で2時間反応
した。反応液中の溶媒及び未反応のアリルグリシジルエ
ーテルを真空蒸発で除去した結果、54.4gの液状生
成物が得られた。実施例1と同様に構造解析した結果、
生成物は原料のヒドロシリコーン化合物のSi−Hの9
5%が実施例1に示す化8に変換した化合物であること
を確認した。[Example 3] Into the same apparatus as in Example 1, 74.8 g (656 mmol) of allyl glycidyl ether, 0.6 g of a 5% isopropanol solution of chloroplatinic acid hexahydrate, and 95 g of toluene were placed, and the temperature was lowered while stirring. The temperature was raised to 80°C. 20 g (328 mmol of Si--H groups) of a hydrosilicone compound having the structural formula shown in Chemical Formula 10 below was dropped into the flask over 20 minutes. After the dropwise addition was completed, the reaction was carried out at 80° C. for 2 hours. As a result of removing the solvent and unreacted allyl glycidyl ether in the reaction solution by vacuum evaporation, 54.4 g of a liquid product was obtained. As a result of structural analysis similar to Example 1,
The product is Si-H9 of the raw material hydrosilicone compound.
It was confirmed that 5% was the compound converted to Formula 8 shown in Example 1.
【0025】[0025]
【化10】[Chemical formula 10]
【0026】[0026]
【応用例】実施例1〜3で得られたシリコーン含有エポ
キシ化合物とメチルメタクリレート/n−ブチルアクリ
レート/3−メタクリロキシプロピルトリメトキシシラ
ンの3元共重合体(モル比2/1/0.28)を各々表
1で示す配合で混合し、さらにジブチルスズジラウレー
ト2%(固型分に対して)を加えて混合し、ブリキ板上
に膜厚が30μになるように塗布した。室温で放置する
といづれも約30分間でタックフリーとなり,7日後に
は完全に硬化した。表面光沢はいづれもすぐれていた。[Application example] Silicone-containing epoxy compounds obtained in Examples 1 to 3 and terpolymer of methyl methacrylate/n-butyl acrylate/3-methacryloxypropyltrimethoxysilane (molar ratio 2/1/0.28 ) were mixed in the formulations shown in Table 1, and 2% dibutyltin dilaurate (based on the solid content) was added and mixed, and the mixture was coated on a tin plate to a film thickness of 30 μm. When left at room temperature, each became tack-free in about 30 minutes and was completely cured after 7 days. All had excellent surface gloss.
【0027】サンシャインウェザーメーターを用いて2
,000時間後の耐候性(光沢保持率)を測定した。
その結果を表2に示す。この結果よりいづれも耐候性が
非常にすぐれていることを確認した。[0027] Using a sunshine weather meter 2
,000 hours later, the weather resistance (gloss retention rate) was measured. The results are shown in Table 2. From these results, it was confirmed that all the materials had excellent weather resistance.
【0028】[0028]
【表1】[Table 1]
【0029】[0029]
【表2】[Table 2]
【0030】[0030]
【発明の効果】本発明のシリコーン含有エポキシ化合物
は、耐候性、耐熱性などのすぐれた塗料、シーリング剤
等の原料として有用である。[Effects of the Invention] The silicone-containing epoxy compound of the present invention is useful as a raw material for paints, sealants, etc., which have excellent weather resistance and heat resistance.
【図1】図1は、実施例1で得られた生成物の 1H−
NMRスペクトルである。FIG. 1 shows 1H- of the product obtained in Example 1.
This is an NMR spectrum.
【図2】図2は、実施例1で得られた生成物の赤外吸収
スペクトルである。FIG. 2 is an infrared absorption spectrum of the product obtained in Example 1.
Claims (2)
ポキシ化合物。 【化1】1. A silicone-containing epoxy compound represented by the following formula 1. [Chemical formula 1]
シリコーン化合物とアクリルグリシジルエーテルとを白
金系触媒の存在下、50〜150℃で反応させることを
特徴とするシリコーン含有エポキシ化合物の製法。 【化2】2. A method for producing a silicone-containing epoxy compound, which comprises reacting a ladder-type hydrosilicone compound represented by the following formula 2 with acrylic glycidyl ether at 50 to 150°C in the presence of a platinum catalyst. [Case 2]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP904991A JPH04252228A (en) | 1991-01-29 | 1991-01-29 | Silicone-containing epoxy compound and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP904991A JPH04252228A (en) | 1991-01-29 | 1991-01-29 | Silicone-containing epoxy compound and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04252228A true JPH04252228A (en) | 1992-09-08 |
Family
ID=11709786
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP904991A Withdrawn JPH04252228A (en) | 1991-01-29 | 1991-01-29 | Silicone-containing epoxy compound and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04252228A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1058730C (en) * | 1994-01-21 | 2000-11-22 | 中国科学院化学研究所 | High-regularity ladder polyhydric sesquisiloxane and its copolymer and preparing method thereof |
US6218497B1 (en) | 1997-04-21 | 2001-04-17 | Alliedsignal Inc. | Organohydridosiloxane resins with low organic content |
JP5050310B2 (en) * | 2000-03-31 | 2012-10-17 | 日立化成工業株式会社 | Method for producing novel silicone polymer, silicone polymer produced by the method, thermosetting resin composition, resin film, metal foil with insulating material, insulating film with double-sided metal foil, metal-clad laminate, multilayer metal-clad Laminated board and multilayer printed wiring board |
JP2017226746A (en) * | 2016-06-22 | 2017-12-28 | 株式会社ダイセル | Silsesquioxane |
-
1991
- 1991-01-29 JP JP904991A patent/JPH04252228A/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1058730C (en) * | 1994-01-21 | 2000-11-22 | 中国科学院化学研究所 | High-regularity ladder polyhydric sesquisiloxane and its copolymer and preparing method thereof |
US6218497B1 (en) | 1997-04-21 | 2001-04-17 | Alliedsignal Inc. | Organohydridosiloxane resins with low organic content |
JP5050310B2 (en) * | 2000-03-31 | 2012-10-17 | 日立化成工業株式会社 | Method for producing novel silicone polymer, silicone polymer produced by the method, thermosetting resin composition, resin film, metal foil with insulating material, insulating film with double-sided metal foil, metal-clad laminate, multilayer metal-clad Laminated board and multilayer printed wiring board |
JP2017226746A (en) * | 2016-06-22 | 2017-12-28 | 株式会社ダイセル | Silsesquioxane |
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