JPS6356529A - Novel titanosiloxane polymer and production thereof - Google Patents
Novel titanosiloxane polymer and production thereofInfo
- Publication number
- JPS6356529A JPS6356529A JP20087686A JP20087686A JPS6356529A JP S6356529 A JPS6356529 A JP S6356529A JP 20087686 A JP20087686 A JP 20087686A JP 20087686 A JP20087686 A JP 20087686A JP S6356529 A JPS6356529 A JP S6356529A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acetylacetonate
- bis
- titanosiloxane
- reaction
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- KVIKMJYUMZPZFU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O KVIKMJYUMZPZFU-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229920000592 inorganic polymer Polymers 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規のチタノシロキサン重合体及びその製造
法に関する。本発明のチタノシロキサン重合体は、常温
で非ゲル状の固体であって急激なゲル化を起さない安定
性を有する。この重合体は、更に加水分解及び縮合反応
させること（より、或いは加熱下縮合反応させることに
よシ、チタン原子、珪素原子及び酸素原子からなる無機
質の酸化物硬化体に変る性質を有し、無機繊維、無機コ
ーティング剤、無機接着剤、無機結合剤等の原料又はそ
の成分として用いられる。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel titanosiloxane polymer and a method for producing the same. The titanosiloxane polymer of the present invention is a non-gel solid at room temperature and has stability that does not cause rapid gelation. This polymer has the property of converting into an inorganic oxide cured product consisting of titanium atoms, silicon atoms and oxygen atoms by further hydrolysis and condensation reaction (or by condensation reaction under heating), It is used as a raw material or component of inorganic fibers, inorganic coating agents, inorganic adhesives, inorganic binders, etc.
（従来の技術）
ポリチタノシロキサンに関しては、ポリチタノメチルシ
ロキサン等耐熱性のポリチタノオルガノシロキサンが既
に、ジャーナル・オプ・ポリマー・サイｘ ：／ ス（
Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ ５ｃｉｅｎ−
ｃｅ）第５２巻第２５７〜２７６頁（１’６１年）に記
載されており、また窯業協会誌第８４巻第６１４〜６１
８頁（１９７６年）にも、シリコンテトラエトキシドと
チタンテトラインプロポキシドとの共加水分解によって
生成することが示されている。(Prior art) Regarding polytitanosiloxanes, heat-resistant polytitanoorganosiloxanes such as polytitanomethylsiloxane have already been published in the Journal of Polymer Sci.
Journal of Polymer 5cien-
ce) Vol. 52, pp. 257-276 (1'61), and Ceramics Association Journal, Vol. 84, pp. 614-61.
8 (1976) also shows that it is produced by cohydrolysis of silicon tetraethoxide and titanium tetrane propoxide.
（発明が解決しようとする問題点）
ポリチタノオルガノシロキサンは、高価な有機珪素化合
物を原料とし、また、その生成反応及び製造方法が複雑
である。更にこのポリマーには、炭素−珪素の直接結合
が存するために、低温ではとのポリマーを完全に無機化
することができない。(Problems to be Solved by the Invention) Polytitanoorganosiloxane uses an expensive organic silicon compound as a raw material, and its production reaction and manufacturing method are complicated. Furthermore, since this polymer contains direct carbon-silicon bonds, it is not possible to completely mineralize the polymer at low temperatures.
一方、シリコンテトラエトキシドとチタンテトラインプ
ロポキシドの共加水分解によって生成スるポリチタノシ
ロキサンは、極めて不安定であって、縮合反応の進行に
よるゲル化を起し易い。例えば、有用性が高い曳糸性を
示す状態にある期間は約１時間以内であるから、これを
工業製品として提供することは困難である。従って、こ
れを用いることによっては、品質一定の無機繊維、塗料
、接着剤等は得られない。On the other hand, polytitanosiloxane produced by co-hydrolysis of silicon tetraethoxide and titanium tetrane propoxide is extremely unstable and tends to gel due to the progress of the condensation reaction. For example, it is difficult to provide this as an industrial product because the period in which it is in a state where it exhibits highly useful stringiness is about one hour or less. Therefore, by using this, inorganic fibers, paints, adhesives, etc. of constant quality cannot be obtained.
本発明の目的は、常温での安定性は高いが、容易に完全
無機化せしめ得る非ゲル状チタノシロキサン重合体及び
その製造方法を提供することにある。An object of the present invention is to provide a non-gel titanosiloxane polymer that is highly stable at room temperature but can be easily completely mineralized, and a method for producing the same.
（問題点を解決するための手段）
本発明の安定性が高い非ゲル状のチタノシロキサン重合
体は、珪酸とビス（アセチルアセトネート）チタンジイ
ソプロポキシドｆ 、８１０２／Ｔｉｅ、モル比１１２
５〜４の比率に反応させることによって得られる。(Means for Solving the Problems) The highly stable non-gel titanosiloxane polymer of the present invention is composed of silicic acid and bis(acetylacetonate) titanium diisopropoxide f, 8102/Tie, molar ratio 112.
It is obtained by reacting at a ratio of 5 to 4.
本発明に用いられる珪酸は、従来から知られている方法
によって容易に得られ、例えば、水ガラス、メタ珪酸ソ
ーダ、珪酸アンモニウム等可溶性珪酸塩の水溶液を酸に
よって中和処理することによシ、或いは陽イオン交換樹
脂で処理することによシ水溶液として得られる。The silicic acid used in the present invention can be easily obtained by a conventionally known method, for example, by neutralizing an aqueous solution of a soluble silicate such as water glass, sodium metasilicate, or ammonium silicate with an acid. Alternatively, it can be obtained as an aqueous solution by treatment with a cation exchange resin.
本発明のチタノシロキサン重合体の生成反応には、上記
例示の如き処理で得られた水溶液を、テトラヒドロフラ
ンで抽出処理するととによシ得られる珪酸のテトラヒド
ロフラン溶液が用いられる。In the production reaction of the titanosiloxane polymer of the present invention, a tetrahydrofuran solution of silicic acid is used, which is obtained by extracting the aqueous solution obtained by the above-mentioned treatment with tetrahydrofuran.
本発明のチタノシロキサン重合体は、上記珪酸のテトラ
ヒドロフラン溶液にビス（アセチルアセトネート）チタ
ンジイソプロポキシド全上記モル比に加えて室温〜溶媒
の還流温度で反応させることによシ容易に生成する。こ
の反応はメタノール、エタノール、イソプロパツール等
の溶媒中で行わせることもできる。反応時間としては、
１１５〜１２時間程度でよい。The titanosiloxane polymer of the present invention can be easily produced by adding bis(acetylacetonate)titanium diisopropoxide in the above molar ratio to a tetrahydrofuran solution of the silicic acid mentioned above and reacting it at room temperature to the reflux temperature of the solvent. do. This reaction can also be carried out in a solvent such as methanol, ethanol, isopropanol, or the like. The reaction time is
It may take about 115 to 12 hours.
メタノール中で反応させると、この反応の後に溶媒を留
去させることによシ重合体の濃縮液が得られる。この濃
縮液にガラス棒を接触させた後引き上げると、液は曳糸
性を示し、本発明の非ゲル状のチタノシロキサン重合体
の繊維が得られる。また、テトラヒドロフラン中での反
応では、本発明の非ゲル状チタノシロキサン重合体は沈
澱物として生成するが、これを取り出しメタノール又は
エタノールに加えると溶解する。この溶液をヘキサン等
非溶媒中に投入すると再び沈澱物が生じ、これを回収す
ると粉状物が得られる。When the reaction is carried out in methanol, a concentrated liquid of the polymer can be obtained by distilling off the solvent after the reaction. When a glass rod is brought into contact with this concentrated liquid and then pulled up, the liquid exhibits stringiness and the non-gel titanosiloxane polymer fiber of the present invention is obtained. Further, in the reaction in tetrahydrofuran, the non-gelled titanosiloxane polymer of the present invention is produced as a precipitate, but when this is taken out and added to methanol or ethanol, it dissolves. When this solution is poured into a non-solvent such as hexane, a precipitate is formed again, and when this is collected, a powder is obtained.
（作 用）
本発明により、珪酸とビス（アセデルアセトネート）チ
タンジイソプロポキシドを反応させると、ビス（アセチ
ルアセトネート）チタノシロキサン結合（Ｔｉ −（Ｊ
−８ｉ ）による重合体が生成する。このチタノシロキ
サン結合は、上記粉状物の赤外線吸収スペクトルに９３
０１Ｍ の吸収ピークが表わされることにより確認され
た。また、１５２０〜１５ Ｂ Ｄａｍ−’にもカルボ
ニル基に基ずく吸収が観測された。(Function) According to the present invention, when silicic acid and bis(acetylacetonate) titanium diisopropoxide are reacted, a bis(acetylacetonate)titanosiloxane bond (Ti-(J
-8i) is produced. This titanosiloxane bond shows 93% in the infrared absorption spectrum of the powder.
This was confirmed by the appearance of an absorption peak of 0.01M. Further, absorption based on carbonyl group was also observed in 1520-15 B Dam-'.
しかし、本発明の非ゲル状のビス（アセチルアセトネー
ト）チタノシロキサン重合体は、珪酸トビス（アセチル
アセトネート）チタンジイソプロポキシドの反応モル比
が５ｉｎＬ／Ｔｉｅ、として４ｔ″越えると得られない
。このモル比４以上では溶媒に不溶のゲルが生成する。However, the non-gel bis(acetylacetonate) titanosiloxane polymer of the present invention can be obtained when the reaction molar ratio of tobis(acetylacetonate)titanium diisopropoxide silicate exceeds 4t'' as 5 inL/Tie. No. If the molar ratio is 4 or more, a gel insoluble in the solvent will be formed.
このモル比がα２５〜４であるとメタノール、エタノー
ル等の溶媒に溶ける生成物となシ、曳糸性を示す。When this molar ratio is α25 to 4, the product is soluble in solvents such as methanol and ethanol, and exhibits stringiness.
本発明のチタノシロキサン重合体は、上記原料成分の珪
酸とビス（アセチルアセトネート）チタンジイソプロポ
キシドをテトラヒドロ７ラン又はメタノール中で反応さ
せることにょ）円滑に収率よく生成せしめ得る。The titanosiloxane polymer of the present invention can be produced smoothly and in good yield by reacting the above-mentioned raw material components silicic acid and bis(acetylacetonate)titanium diisopropoxide in tetrahydro7rane or methanol.
（実施例）
実施例ｌ
５ｉＯ！トしてα８５モル／ｌの珪酸のテトラヒドロフ
２ン溶液囚１１．８−と、Ｓ ｉ Ｏｘ／ Ｔｉ ０２
モル比が１となるようにビス（アセチルアセトネート）
チタンジイソプロポキシド＠１６ｔ２メタノール２０−
に加え、溶媒の還流下（Ｌ５時間反応させることによシ
粘稠な反応混合物を得た。この溶液から溶媒を留去する
と濃縮液が得られ、これにガラス棒を接触させた後引き
上げると曳糸性を示した。別途、上記濃縮液全エタノー
ルに加えると溶液が得られ、これを多量のへキサン中に
投入したところ、沈澱が生じた。この沈澱を回収し、乾
燥することにより２．５２の粉末を得た。(Example) Example 1 5iO! and α85 mol/l of silicic acid in tetrahydrofuran solution 11.8-, and S i Ox/Ti 02
Bis(acetylacetonate) so that the molar ratio is 1
Titanium diisopropoxide @16t2 methanol 20-
In addition, a viscous reaction mixture was obtained by reacting for 5 hours under reflux of the solvent. When the solvent was distilled off from this solution, a concentrated liquid was obtained, which was brought into contact with a glass rod and pulled up. It exhibited stringiness. Separately, when the above concentrated solution was added to total ethanol, a solution was obtained, and when this was poured into a large amount of hexane, a precipitate was formed. This precipitate was collected and dried to obtain a solution. A powder of .52 was obtained.
上記粉末を赤外線吸収スペクトル分析したところ、９５
０傭 にチタノシロキサン結合に基ずく吸収と、１５２
０〜１５８０ｃＩＮ にカルボニル基に基づく吸収が観
測された。When the above powder was analyzed by infrared absorption spectrum, it was found that 95
Absorption based on titanosiloxane bonds and 152
Absorption based on carbonyl groups was observed at 0 to 1580 cIN.
実施例２
実施例１に用いられたものと同じ原料囚と（ハ）とを、
第１表に記載の量用い九他は、実施例１曳糸性としてｔ
ａ維長を測定すると共に、この混合液の性状及び回収さ
れたチタノシロキサン重合体の収！？第１表に示す。Example 2 The same raw materials and (c) as used in Example 1 were
The amounts listed in Table 1 were used in Example 1.
a.Measure the fiber length, as well as the properties of this mixture and the yield of the recovered titanosiloxane polymer. ? Shown in Table 1.
第 １ 表
１ ！Ｌ？ ７．２ （Ｌ２５ 粘
稠液 ５１．３２ ５９ 己６ α５０
粘稠液 ３０ｔ７３２五５五６ ２．００ 樹脂
２ 五９４４Ｚ１五６ 瓜００ 樹脂 −！Ｌ？実施
例３
上記と同じ固液及び■液金用い、第１表記載の如＜ ８
ｉ ０．／ Ｔｉ Ｏ，モル死別に反応時間を変えた他
は実施例１と同様にして実験巡１〜１５の反応混合液を
得、曳糸性を測定した。結果を第２表に示す。 ４
１ α２５ １
５０５ （Ｌ２５ ４
５０４ （Ｌ２５
８ ５０５ ｃＬ２
５ １２ ５０６
（Ｌ５ １ ６Ｑ７
α５ ２ ５
０８ α５ ４ ５
０９ Ｉ１５ ８
１８０１０ α５
１２ １００１１ １．０
１ ５１２
１．０ ２ ０１
！５ ２．０ １
０実施例４
メタノール溶媒を用いない他は、実施例１と同様にして
、Ｓ＋ ０２７ Ｔｔ Ｏｔモル比１となるように原料
囚に＠を加えて反応させたところ、沈澱が生じた。直ち
に、この沈澱物を回収し、メタノールに加えたところ溶
解した。この溶液をヘキサン中に投入したととる、再び
沈澱が生じた。1st table 1! L? 7.2 (L25 viscous liquid 51.32 59 self 6 α50
Viscous liquid 30t7325556 2.00 Resin
2 5944Z156 Melon 00 Resin -! L? Example 3 Using the same solid-liquid and liquid gold as above, as shown in Table 1 < 8
i0. The reaction mixtures of Experiments 1 to 15 were obtained in the same manner as in Example 1, except that the reaction time was changed depending on the amount of TiO and molar separation, and the stringiness was measured. The results are shown in Table 2. 4 1 α25 1
505 (L25 4
504 (L25
8 505 cL2
5 12 506
(L5 1 6Q7
α5 2 5
08 α5 4 5
09 I15 8
18010 α5
12 10011 1.0
1 512
1.0 2 01
! 5 2.0 1
Example 4 In the same manner as in Example 1 except that the methanol solvent was not used, @ was added to the raw materials so that the molar ratio of S+ 027 Tt Ot was 1, and reaction was caused, resulting in precipitation. This precipitate was immediately collected and dissolved in methanol. When this solution was poured into hexane, precipitation occurred again.
別途、Ｓｉ ０２／ ＴｉＯ２モル比全１２５．α５．
２．０及び４．０に変えて上記と同様に反応させたが、
やはり沈澱が生じ、この沈澱物はメタノールに溶解した
。とれらメタノール溶液をヘキサン中に投入すると、再
び沈澱が生じた。Separately, Si02/TiO2 molar ratio total 125. α5.
2.0 and 4.0 were changed and the reaction was carried out in the same manner as above, but
Again, a precipitate formed and this precipitate was dissolved in methanol. When the methanol solution was poured into hexane, precipitation occurred again.
上記ヘキサン中の沈澱物を回収し、赤外線吸収スペクト
ル分析を行ったところ、９３０ｃｒＲにＴｉ−０−８ｉ
結合の吸収を、また、１５２０〜１５８０ｔＭｔ−’に
は二〇＝０結合の吸収を観測した。別途上記回収沈澱物
について灰分量を測定したところ、５５〜６３重量％で
あった。When the precipitate in hexane was collected and subjected to infrared absorption spectrum analysis, Ti-0-8i was found to be 930crR.
Absorption of binding was observed, and absorption of 20=0 binding was observed from 1520 to 1580 tMt-'. The ash content of the recovered precipitate was separately measured and found to be 55 to 63% by weight.
（発明の効果）
本発明によると、珪酸とビス（アセチルアセトネート）
テタンジイソグロポキシド＝ｉＳｉ０２／ＴｉＯ２モル
比４以下で溶媒中で反応させるのみで、容易に非ゲル状
のビス（アセチルアセトネート）チタノシロキサン重合
体が得られる。この重合体は急激なゲル化が起らないの
で、安定な工業製品としての生産が可能である。(Effect of the invention) According to the invention, silicic acid and bis(acetylacetonate)
A non-gel bis(acetylacetonate) titanosiloxane polymer can be easily obtained simply by reacting in a solvent at a molar ratio of tetanediisogropoxide=iSi02/TiO2 of 4 or less. Since this polymer does not undergo rapid gelation, it can be produced as a stable industrial product.
Claims (3)
シロキサン重合体。(1) Non-gel bis(acetylacetonate) titanosiloxane polymer.
ソプロポキシドを反応させることを特徴とする非ゲル状
のビス（アセチルアセトネート）チタノシロキサン重合
体の製造法。(2) A method for producing a non-gel bis(acetylacetonate) titanosiloxane polymer, which comprises reacting silicic acid with bis(acetylacetonate) titanium diisopropoxide.
チタンジイソプロポキシドの比率を、ＳｉＯ＿２／Ｔｉ
Ｏ＿２モル比として０．２５〜４とする特許請求の範囲
第（２）項に記載の非ゲル状のビス（アセチルアセトネ
ート）チタノシロキサン重合体の製造法。(3) Silicic acid and bis(acetylacetonate) to be reacted
The ratio of titanium diisopropoxide was changed to SiO_2/Ti
A method for producing a non-gel bis(acetylacetonate) titanosiloxane polymer according to claim (2), wherein the O_2 molar ratio is 0.25 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20087686A JPS6356529A (en) | 1986-08-27 | 1986-08-27 | Novel titanosiloxane polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20087686A JPS6356529A (en) | 1986-08-27 | 1986-08-27 | Novel titanosiloxane polymer and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6356529A true JPS6356529A (en) | 1988-03-11 |
| JPH0314853B2 JPH0314853B2 (en) | 1991-02-27 |
Family
ID=16431706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20087686A Granted JPS6356529A (en) | 1986-08-27 | 1986-08-27 | Novel titanosiloxane polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6356529A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009052011A (en) * | 2007-07-27 | 2009-03-12 | Dic Corp | Organic-inorganic hybrid resin aqueous dispersion, curable resin composition, paint and paint |
| US9152052B2 (en) | 2011-08-11 | 2015-10-06 | Merck Patent Gmbh | Composition for forming tungsten oxide film and method for producing tungsten oxide film using same |
| US9201305B2 (en) | 2013-06-28 | 2015-12-01 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin-on compositions of soluble metal oxide carboxylates and methods of their use |
| US9296922B2 (en) | 2013-08-30 | 2016-03-29 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds as hardmasks and filling materials, their compositions and methods of use |
| US9315636B2 (en) | 2012-12-07 | 2016-04-19 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds, their compositions and methods |
| US9409793B2 (en) | 2014-01-14 | 2016-08-09 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin coatable metallic hard mask compositions and processes thereof |
| US9499698B2 (en) | 2015-02-11 | 2016-11-22 | Az Electronic Materials (Luxembourg)S.A.R.L. | Metal hardmask composition and processes for forming fine patterns on semiconductor substrates |
| US11042091B2 (en) | 2017-09-06 | 2021-06-22 | Merck Patent Gmbh | Spin-on inorganic oxide containing composition useful as hard masks and filling materials with improved thermal stability |
-
1986
- 1986-08-27 JP JP20087686A patent/JPS6356529A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009052011A (en) * | 2007-07-27 | 2009-03-12 | Dic Corp | Organic-inorganic hybrid resin aqueous dispersion, curable resin composition, paint and paint |
| US9152052B2 (en) | 2011-08-11 | 2015-10-06 | Merck Patent Gmbh | Composition for forming tungsten oxide film and method for producing tungsten oxide film using same |
| US9315636B2 (en) | 2012-12-07 | 2016-04-19 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds, their compositions and methods |
| US9201305B2 (en) | 2013-06-28 | 2015-12-01 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin-on compositions of soluble metal oxide carboxylates and methods of their use |
| US9296922B2 (en) | 2013-08-30 | 2016-03-29 | Az Electronic Materials (Luxembourg) S.A.R.L. | Stable metal compounds as hardmasks and filling materials, their compositions and methods of use |
| US9409793B2 (en) | 2014-01-14 | 2016-08-09 | Az Electronic Materials (Luxembourg) S.A.R.L. | Spin coatable metallic hard mask compositions and processes thereof |
| US9499698B2 (en) | 2015-02-11 | 2016-11-22 | Az Electronic Materials (Luxembourg)S.A.R.L. | Metal hardmask composition and processes for forming fine patterns on semiconductor substrates |
| US11042091B2 (en) | 2017-09-06 | 2021-06-22 | Merck Patent Gmbh | Spin-on inorganic oxide containing composition useful as hard masks and filling materials with improved thermal stability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0314853B2 (en) | 1991-02-27 |
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