JPS643121B2 - - Google Patents
Info
- Publication number
- JPS643121B2 JPS643121B2 JP13306682A JP13306682A JPS643121B2 JP S643121 B2 JPS643121 B2 JP S643121B2 JP 13306682 A JP13306682 A JP 13306682A JP 13306682 A JP13306682 A JP 13306682A JP S643121 B2 JPS643121 B2 JP S643121B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- reference example
- group
- acid fluoride
- glycol
- 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 239000002253 acid Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000002518 antifoaming agent Substances 0.000 description 8
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- -1 polydimethylsiloxane Polymers 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000001577 simple distillation Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Chemical compound 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical class FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 4
- XZNOAVNRSFURIR-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol Chemical compound FC(F)(F)C(O)(C(F)(F)F)C(F)(F)F XZNOAVNRSFURIR-UHFFFAOYSA-N 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical compound FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Degasification And Air Bubble Elimination (AREA)
Description
本発明は、消泡剤に関する。更に詳しくは、有
機溶剤による起泡に対する抑制効果の点で特にす
ぐれている消泡剤に関する。
従来から、種々の消泡剤が多数提案されてお
り、例えば(1)ポリジメチルシロキサン、ポリフエ
ニルメチルシロキサン、ポリプロピルメチルシロ
キサンなどを主成分とするもの、あるいはこれら
を炭化水素油、ポリエーテル油などのオイル組成
物としたものまたは微粉末シリカなどとのコンパ
ウンドしたものなどのシリコーン系消泡剤（特公
昭47−13487号公報、同42−22455号公報、特開昭
49−109276号公報、同48−36084号公報参照）、(2)
ポリエチレングリコール、コーポリ（エチレング
リコール・プロピレングリコール）などのポリア
ルキレングリコール（特公昭50−1475号公報参
照）、(3)多価金属石けん（特公昭42−11328号公報
参照）、(4)アルキルリン酸エステルまたはアルキ
ル亜リン酸エステル（特公昭47−12177号公報参
照）などが挙げられる。
これらは、いずれも水性系の溶液およびエマル
ジヨンの消泡を主たる対象としており、一部に有
機溶剤溶液を対象にしているものもみられるが、
その効果はわずかである。即ち、これらの消泡剤
は、水／炭化水素系界面活性剤による泡を消すこ
とができるものの、より表面張力の小さい有機溶
媒系の泡を消すことはできない。また、通常のフ
ツ素系界面活性剤で、下記のような構造を有する
ものについても、有機溶剤系の泡を消す効果は、
格別すぐれているものとはいえない。
Rf−Ｒ Rr：疎油性基（または疎水性基）
Ｒ：親油性基（または親水性基）
本発明者は、水性系の溶媒およびエマルジヨン
については勿論のこと、有機溶剤溶液に対しても
これらから生ずる起泡に対して十分な抑制効果を
示すフツ素系化合物について種々検討の結果、一
般式
（ここで、Ｘはフツ素原子または水素原子であ
り、Ｙはフツ素原子またはトリフルオロメチル基
であり、ｍは１以上の整数、一般には１〜５であ
り、そしてｎは０または１以上の整数、一般には
０〜約50である）で表わされるパーフルオロエー
テル化合物がきわめて有効であることを見出し
た。
かかるパーフルオロエーテル化合物は、ヘキサ
フルオロプロピレンオキシドおよびオクタフルオ
ロイソブテンオキシドの少くとも１種を単独で、
あるいはパーフルオロ第３ブタノール、ヘキサフ
ルオロアセトン、トリフルオロ酢酸フロライド、
カルボニルフロライドなどを反応の開始剤に用い
て、重合して得られるポリ（パーフルオロアルキ
レングリコール）の酸フロライドを、フツ素ガス
で処理することによりフツ素化物として、あるい
はエチレングリコールおよび水酸化ナトリウム水
溶液で処理することにより水素化物としてそれぞ
れ得られる。
これらの各種ポリ（パーフルオロエーテル）化
合物の合成において、出発物質として用いられる
酸フロライドを分留して用いることにより、所望
するｎの値を有する化合物を得ることができる。
そして、ｎの値としては、一般に０〜約50の範囲
のものが用いられ、特に約１〜50の範囲のものが
好ましい。
これらのポリ（パーフルオロエーテル）化合物
は、水性系の溶液またはエマルジヨン、有機溶剤
溶液、重合体溶液、特に塗料などに対し、それ単
独であるいは必要に応じてシリコンオイル、ポリ
エチレングリコール、ポリアミドなどと混合して
添加することにより、いずれもすぐれた消泡効果
が得られる。
好ましいポリ（パーフルオロエーテル）化合物
を構造的な面からみると、末端のパーフルオロア
ルキル基については（CF3）3CO−基、
（CF3）2CFO−基が最も好ましく、CF3CF2O−基、
CF3O−基はCF3CF2CF2O−基よりやや好ましく、
また中間のパーフルオロアルキレングリコール基
についてもＹ＝ＦのものよりはＹ＝CF3のものの
方が好ましいなど、分岐の多い構造のものがより
良好な消泡効果を示している。
次に、実施例について本発明の効果を説明す
る。なお、各参考例は、消泡剤化合物の合成法を
述べたものである。
参考例 １
パーフルオロ第３ブタノール236ｇに炭酸セシ
ウム162ｇを加え、溶媒として用いたジオキサン
（500ml）の還流下に４時間反応させた。その後、
減圧下でジオキサンを留去し、残渣を100℃で真
空乾燥する。
このようにして得られたセシウム パーフルオ
ロ第３ブトキサイドの一部36.7ｇに、ヘキサフル
オロプロピレンオキシド84ｇおよび無水のアセト
ニトリル50mlを加え、−10℃で48時間重合反応さ
せた。反応混合物を無水のフツ化水素で処理し、
単蒸留（沸点85〜120℃／0.3〜0.4mmHg）を行な
つた。Ｆ−NMRスペクトルおよび赤外線吸収ス
ペクトルの測定結果から、下記構造の酸フロライ
ドが得られたものと考えられる。
参考例 ２
ヘキサフルオロアセトン166ｇ、ヘキサフルオ
ロプロピレンオキシド720ｇ、フツ化セシウム
12.9ｇおよびジエチレングリコール100ｇの混合
物を、オートクレーブ中−10℃で48時間重合反応
させる。得られた反応混合物を、無水のフツ化水
素で処理し、単蒸留（沸点80〜98℃／0.4mmHg）
を行なつた。Ｆ−NMRスペクトルおよび赤外線
吸収スペクトルの測定結果から、下記構造の酸フ
ロライドが得られるものと考えられる。
参考例 ３
トリフルオロ酢酸フロライド116ｇ、ヘキサフ
ルオロプロピレンオキシド370ｇ、フツ化セシウ
ム15.5ｇおよびジエチレングリコール100ｇの混
合物を、オートクレーブ中−10℃で48時間重合反
応させる。得られた反応混合物を、無水のフツ化
水素で処理し、単蒸留（沸点96〜108℃／７〜８
mmHg）を行なつた。Ｆ−NMRスペクトルおよ
び赤外線吸収スペクトルの測定結果から、下記構
造の酸フロライドが得られたものと考えられる。
参考例 ４
参考例３において、トリフルオロ酢酸フロライ
ドの代りに、カルボニルフロライド66ｇが用いら
れた。分留された単蒸留物（沸点142〜163℃）
は、Ｆ−NMRスペクトルおよび赤外線吸収スペ
クトルの測定結果から、下記構造の酸フロライド
と考えられる。
参考例 ５
オクタフルオロイソブテンオキシド216ｇ、フ
ツ化セシウム14.2ｇおよびテトラエチレングリコ
ールジメチルエーテル100mlの混合物を、オート
クレーブ中−10℃で48時間重合反応させる。得ら
れた反応混合物を、無水のフツ化水素で処理し、
単蒸留（沸点91〜107℃／0.4mmHg）を行なつた。
Ｆ−NMRスペクトルおよび赤外線吸収スペクト
ルの測定結果から、下記構造の酸フロライドと考
えられる。
参考例 ６
ヘキサフルオロプロピレンオキシド166ｇ、フ
ツ化セシウム5.7ｇおよびアセトニトリル100mlの
混合物を、オートクレーブ中−20℃で48時間重合
反応させる。得られた反応混合物を、無水のフツ
化水素で処理し、単蒸留を行ない、沸点200℃以
上／0.5mmHgの釜残を得た。Ｆ−NMRスペクト
ルおよび赤外線吸収スペクトルの測定結果から、
下記構造の酸フロライドと考えられる。
参考例 ７
参考例６で得られた酸フロライドを、特公昭
38−12197号公報記載の方法に準じてフツ素ガス
で処理し、反応生成物を分留して、次式で示され
るフツ素化物およびを得た。
参考例 ８
参考例６で得られた酸フロライドを、特公昭
39−24872号公報記載の方法に準じてエチレング
リコールおよび水酸化ナトリウム水溶液で処理
し、次いで反応生成物を分留し、次式で示される
水素化物およびを得た。
実施例 １
パーフルオロオクチルエチルアクリレート−２
−エチルヘキシルアクリレート（重量比70：30）
共重合体の10％メチルクロロホルム溶液を、パー
クロルエチレンで0.5％濃度に希釈し、この希釈
溶液10mlを容量25mlの栓付試験管に入れる。そこ
に、前記各参考例の化合物を共重合体に対して
0.05重量％消泡剤として加え、10回激しく振とう
し、その直後と60秒後の泡の高さ（直径20mmの円
筒状試験管での泡部分の容積を0.5ml単位で示す）
を測定し、その消泡効果を評価した。得られた結
果は、次の表１に示される。なお、No.５〜９は比
較例である。
The present invention relates to antifoaming agents. More specifically, the present invention relates to an antifoaming agent that is particularly excellent in suppressing foaming caused by organic solvents. A large number of various antifoaming agents have been proposed in the past, such as (1) those containing polydimethylsiloxane, polyphenylmethylsiloxane, polypropylmethylsiloxane, etc. as main components, or those containing these as main components, such as hydrocarbon oils, polyether oils, etc. Silicone antifoaming agents such as those made into oil compositions such as those or those compounded with finely powdered silica etc.
49-109276, 48-36084), (2)
Polyalkylene glycols such as polyethylene glycol and copoly (ethylene glycol/propylene glycol) (see Japanese Patent Publication No. 1475-1975), (3) Polyvalent metal soaps (see Japanese Patent Publication No. 11328-1977), (4) Alkylins Examples include acid esters and alkyl phosphite esters (see Japanese Patent Publication No. 12177/1983). All of these are mainly aimed at defoaming aqueous solutions and emulsions, and some are also aimed at organic solvent solutions.
The effect is small. That is, although these antifoaming agents can eliminate foam caused by water/hydrocarbon surfactants, they cannot eliminate foam caused by organic solvents, which have a lower surface tension. In addition, ordinary fluorine-based surfactants with the structure shown below have the effect of eliminating organic solvent-based foam.
It cannot be said that it is particularly excellent. Rf-R Rr: Lipophobic group (or hydrophobic group) R: Lipophilic group (or hydrophilic group) The present inventor has determined that these groups can be used not only for aqueous solvents and emulsions, but also for organic solvent solutions. As a result of various studies on fluorine-based compounds that have a sufficient suppressive effect on foaming caused by (wherein, It has been found that perfluoroether compounds having an integer of from 0 to about 50 are very effective. Such a perfluoroether compound contains at least one of hexafluoropropylene oxide and octafluoroisobutene oxide alone,
Or perfluoro tert-butanol, hexafluoroacetone, trifluoroacetic acid fluoride,
The acid fluoride of poly(perfluoroalkylene glycol) obtained by polymerization using carbonyl fluoride etc. as a reaction initiator is treated with fluorine gas to produce a fluorinated product, or ethylene glycol and sodium hydroxide. Each can be obtained as a hydride by treatment with an aqueous solution. In the synthesis of these various poly(perfluoroether) compounds, compounds having a desired value of n can be obtained by fractionating and using the acid fluoride used as a starting material.
The value of n is generally in the range of 0 to about 50, and preferably in the range of about 1 to 50. These poly(perfluoroether) compounds can be used alone or optionally mixed with silicone oil, polyethylene glycol, polyamide, etc., in aqueous solutions or emulsions, organic solvent solutions, polymer solutions, and especially paints. By adding them, excellent antifoaming effects can be obtained. From a structural standpoint, preferred poly(perfluoroether) compounds have terminal perfluoroalkyl groups such as (CF 3 ) 3 CO− group,
( CF3 ) 2CFO- group is most preferred, CF3CF2O- group,
CF 3 O− group is slightly more preferred than CF 3 CF 2 CF 2 O− group,
Furthermore, regarding the intermediate perfluoroalkylene glycol group, those with Y=CF 3 are preferable to those with Y=F, and those with a structure with more branches exhibit better antifoaming effects. Next, the effects of the present invention will be explained with reference to Examples. Note that each reference example describes a method for synthesizing an antifoam compound. Reference Example 1 162 g of cesium carbonate was added to 236 g of perfluoro tert-butanol, and the mixture was reacted for 4 hours under reflux of dioxane (500 ml) used as a solvent. after that,
Dioxane is distilled off under reduced pressure and the residue is vacuum dried at 100°C. 84 g of hexafluoropropylene oxide and 50 ml of anhydrous acetonitrile were added to a portion of 36.7 g of the cesium perfluoro tert-butoxide thus obtained, and a polymerization reaction was carried out at -10°C for 48 hours. treating the reaction mixture with anhydrous hydrogen fluoride;
Simple distillation (boiling point 85-120°C/0.3-0.4 mmHg) was performed. From the measurement results of F-NMR spectrum and infrared absorption spectrum, it is considered that an acid fluoride having the following structure was obtained. Reference example 2 Hexafluoroacetone 166g, hexafluoropropylene oxide 720g, cesium fluoride
A mixture of 12.9 g and 100 g of diethylene glycol is polymerized in an autoclave at -10°C for 48 hours. The resulting reaction mixture was treated with anhydrous hydrogen fluoride and subjected to simple distillation (boiling point 80-98℃/0.4mmHg).
I did this. From the measurement results of F-NMR spectrum and infrared absorption spectrum, it is thought that an acid fluoride having the following structure can be obtained. Reference Example 3 A mixture of 116 g of trifluoroacetic acid fluoride, 370 g of hexafluoropropylene oxide, 15.5 g of cesium fluoride and 100 g of diethylene glycol is polymerized in an autoclave at -10°C for 48 hours. The resulting reaction mixture was treated with anhydrous hydrogen fluoride and subjected to simple distillation (boiling point 96-108°C/7-8°C).
mmHg) was performed. From the measurement results of F-NMR spectrum and infrared absorption spectrum, it is considered that an acid fluoride having the following structure was obtained. Reference Example 4 In Reference Example 3, 66 g of carbonyl fluoride was used instead of trifluoroacetic fluoride. Fractionated simple distillate (boiling point 142-163℃)
is considered to be an acid fluoride having the following structure from the measurement results of F-NMR spectrum and infrared absorption spectrum. Reference Example 5 A mixture of 216 g of octafluoroisobutene oxide, 14.2 g of cesium fluoride, and 100 ml of tetraethylene glycol dimethyl ether is polymerized in an autoclave at -10°C for 48 hours. The resulting reaction mixture was treated with anhydrous hydrogen fluoride,
Simple distillation (boiling point 91-107°C/0.4 mmHg) was performed.
Based on the measurement results of F-NMR spectrum and infrared absorption spectrum, it is considered to be an acid fluoride with the following structure. Reference Example 6 A mixture of 166 g of hexafluoropropylene oxide, 5.7 g of cesium fluoride and 100 ml of acetonitrile is polymerized in an autoclave at -20°C for 48 hours. The resulting reaction mixture was treated with anhydrous hydrogen fluoride and subjected to simple distillation to obtain a bottom residue with a boiling point of 200° C. or more/0.5 mmHg. From the measurement results of F-NMR spectrum and infrared absorption spectrum,
It is considered to be an acid fluoride with the following structure. Reference Example 7 The acid fluoride obtained in Reference Example 6 was
The reaction product was treated with fluorine gas according to the method described in No. 38-12197, and the reaction product was fractionally distilled to obtain a fluorinated product represented by the following formula. Reference Example 8 The acid fluoride obtained in Reference Example 6 was
The reaction product was treated with ethylene glycol and an aqueous sodium hydroxide solution according to the method described in No. 39-24872, and then the reaction product was fractionally distilled to obtain a hydride represented by the following formula. Example 1 Perfluorooctylethyl acrylate-2
-Ethylhexyl acrylate (weight ratio 70:30)
A 10% solution of the copolymer in methyl chloroform is diluted with perchlorethylene to a concentration of 0.5%, and 10 ml of this diluted solution is placed in a 25 ml stoppered test tube. There, the compounds of each of the above reference examples were added to the copolymer.
Added as 0.05% by weight antifoaming agent, shaken vigorously 10 times, and foam height immediately and 60 seconds later (indicates the volume of foam in a cylindrical test tube with a diameter of 20 mm in units of 0.5 ml)
was measured to evaluate its defoaming effect. The results obtained are shown in Table 1 below. Note that Nos. 5 to 9 are comparative examples.
【表】
９ シリコンオイル 〃 〃
実施例 ２
電気絶縁用シリコンワニス（信越化学製品KR
−255）の５％トルエン溶液を栓付試験管に入れ、
実施例１と同様の消泡効果試験を行なつた。得ら
れた結果は、次の表２に示される。なお、No.５〜
７は比較例である。[Table] 9 Silicone oil 〃 〃
Example 2 Silicon varnish for electrical insulation (Shin-Etsu Chemical KR)
-255) into a test tube with a stopper,
A defoaming effect test similar to that in Example 1 was conducted. The results obtained are shown in Table 2 below. In addition, No. 5~
7 is a comparative example.
【表】
７ シリコンオイル 〃 〃
実施例 ３
アクリルエマルジヨン塗料（エチルアクリレー
トを主成分とする共重合体をノニオン、アニオン
併用界面活性剤で乳化したもの）を、水で固形分
濃度が10％程度になるように希釈し、これを栓付
試験管に入れ、実施例１と同様の消泡効果試験を
行なつた。得られた結果は、次の表３に示され
る。なお、No.３〜７は比較例である。[Table] 7 Silicone oil 〃 〃
Example 3 Acrylic emulsion paint (a copolymer mainly composed of ethyl acrylate emulsified with nonionic and anionic surfactants) was diluted with water to a solid concentration of about 10%, and was placed in a test tube with a stopper, and the same defoaming effect test as in Example 1 was conducted. The results obtained are shown in Table 3 below. Note that Nos. 3 to 7 are comparative examples.
【表】
実施例 ４
ポリウレタンの５％ジメチルホルムアミド溶液
を栓付試験管を入れ、実施例１と同様の消泡効果
試験を行なつた。得られた結果は次の表４に示さ
れる。なお、No.３〜７は比較例である。[Table] Example 4 A test tube with a stopper was charged with a 5% solution of polyurethane in dimethylformamide, and the same defoaming effect test as in Example 1 was conducted. The results obtained are shown in Table 4 below. Note that Nos. 3 to 7 are comparative examples.
【表】【table】
【表】
さ 高さ
No. 消泡剤 (ml) （ml）
[Table] Height
No. Antifoam (ml) (ml)
Claims (1)
り、Ｙはフツ素原子またはトリフルオロメチル基
であり、ｍは１以上の整数であり、そしてｎは０
または１以上の整数である）で表わされるパーフ
ルオロエーテル化合物を有効成分とする消泡剤。[Claims] 1. General formula (Here, X is a fluorine atom or a hydrogen atom, Y is a fluorine atom or a trifluoromethyl group, m is an integer of 1 or more, and n is 0
or an integer of 1 or more) as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13306682A JPS5922611A (en) | 1982-07-30 | 1982-07-30 | Antifoaming agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13306682A JPS5922611A (en) | 1982-07-30 | 1982-07-30 | Antifoaming agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5922611A JPS5922611A (en) | 1984-02-04 |
| JPS643121B2 true JPS643121B2 (en) | 1989-01-19 |
Family
ID=15096033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13306682A Granted JPS5922611A (en) | 1982-07-30 | 1982-07-30 | Antifoaming agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5922611A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8129435B2 (en) | 2009-06-18 | 2012-03-06 | Shin-Etsu Chemical Co., Ltd. | Perfluoropolyether-modified polysiloxane, a method for preparing the same and a defoaming agent comprising the same |
| US8304571B2 (en) | 2009-07-17 | 2012-11-06 | Shin-Etsu Chemical Co., Ltd. | Perfluoropolyether-modified polysiloxane, a method for preparing the same and a defoaming agent comprising the same |
| JP5234057B2 (en) | 2010-06-28 | 2013-07-10 | 信越化学工業株式会社 | Perfluoropolyether group-containing polyether-modified polysiloxane and method for producing the same |
| JP6026859B2 (en) * | 2012-11-16 | 2016-11-16 | 楠本化成株式会社 | Antifoaming improver for waterborne antifoaming agent |
| JP5969360B2 (en) * | 2012-11-19 | 2016-08-17 | 楠本化成株式会社 | Defoamer for water-based paint without volatile matter |
-
1982
- 1982-07-30 JP JP13306682A patent/JPS5922611A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5922611A (en) | 1984-02-04 |
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