JP2699539B2 - Method for producing fluorine-containing urethane compound - Google Patents
Method for producing fluorine-containing urethane compoundInfo
- Publication number
- JP2699539B2 JP2699539B2 JP1081053A JP8105389A JP2699539B2 JP 2699539 B2 JP2699539 B2 JP 2699539B2 JP 1081053 A JP1081053 A JP 1081053A JP 8105389 A JP8105389 A JP 8105389A JP 2699539 B2 JP2699539 B2 JP 2699539B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- urethane compound
- diisocyanate
- producing
- containing urethane
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、含フツ素ウレタン化合物およびその製造方
法に関するものである。Description: TECHNICAL FIELD The present invention relates to a fluorine-containing urethane compound and a method for producing the same.
（従来技術とその問題点） 従来のウレタン樹脂は、合成繊維、合成ゴム、フオー
ム、接着剤、塗料など幅広い産業分野に利用されてい
る。(Prior art and its problems) Conventional urethane resins are used in a wide range of industrial fields such as synthetic fibers, synthetic rubbers, foams, adhesives, and paints.
しかし、従来のウレタン樹脂は、酸、アルカリなどに
対する耐薬品性、耐水性や耐湿性、および耐熱性が悪い
という欠点があつた。これらの欠点を改善するためにポ
リフルオロアルキル基を有したウレタン化合物が検討さ
れている（特開昭53−112855号公報，特開昭54−74000
号公報）、 このポリフルオロアルキル基を有したウレタン化合物
は、低分子量化合物、および高分子量化合物に分類され
るが、低分子量化合物は含フツ素モノアルコールとイソ
シアネートとの反応生成物が多いため２量体、３量体な
どのテロマーは得にくく、低分子量化合物のものが多
く、そのために溶融温度が低く、また撥水、撥油性、特
に柔軟性、加工性などがまだ十分でないといつた欠点が
あつた。However, the conventional urethane resin has disadvantages such as poor chemical resistance to acids, alkalis, and the like, water resistance, moisture resistance, and heat resistance. To improve these drawbacks, urethane compounds having a polyfluoroalkyl group have been studied (JP-A-53-112855, JP-A-54-74000).
The urethane compound having a polyfluoroalkyl group is classified into a low molecular weight compound and a high molecular weight compound. The low molecular weight compound contains a large amount of a reaction product between a fluorine-containing monoalcohol and an isocyanate. It is difficult to obtain telomers such as dimers, trimers, etc., many of which are low molecular weight compounds, so that the melting temperature is low, and the water repellency, oil repellency, especially flexibility, processability, etc. are not enough. There was.
また、高分子量化合物においても、上記の問題は必ず
しも満足されていない。In addition, the above problem is not always satisfied with a high molecular weight compound.
（発明の目的） 本発明者らは上記のような問題点を解決するために鋭
意研究した結果、分子中にエーテル結合を有する含フツ
素ジオールとジイソシアネートとの反応生成物が本発明
の目的に適するものであることを見出し、本発明に到達
した。(Object of the Invention) The present inventors have conducted intensive studies in order to solve the above problems, and as a result, a reaction product of a fluorine-containing diol having an ether bond in a molecule and a diisocyanate is an object of the present invention. The present inventors have found that they are suitable, and arrived at the present invention.
（発明の構成） すなわち本発明は、 （１） 炭素数４〜10のペルフルオロアルキル基と、エ
ーテル結合を分子中に含有し、かつポリマーセグメント
当り、少なくとも１個のウレタン結合を有する含フツ素
ウレタン化合物、 （２） 一般式 （式中Rfは炭素数４〜10のペルフルオロアルキル基、
ｎは１または２の整数） で表される含フツ素ジオールと、ジイソシアネートを反
応させることを特徴とする含フツ素ウレタン化合物の製
造方法、 を提供する。(Constitution of the Invention) That is, the present invention provides: (1) a fluorine-containing urethane containing a perfluoroalkyl group having 4 to 10 carbon atoms and an ether bond in a molecule and having at least one urethane bond per polymer segment. Compound, (2) General formula (Wherein R f is a perfluoroalkyl group having 4 to 10 carbon atoms,
(n is an integer of 1 or 2). A process for producing a fluorine-containing urethane compound, characterized by reacting a diisocyanate with a fluorine-containing diol represented by the following formula:
本発明に係わる一般式（１）で表される含フツ素ジオ
ールにおいて、Rfは炭素数４〜10のペルフルオロアルキ
ル基であり、好ましくは炭素数６〜８のペルフルオロア
ルキル基であり、直鎖、分岐鎖のいずれであつてもよ
い。In the fluorine-containing diol represented by the general formula (1) according to the present invention, R f is a perfluoroalkyl group having 4 to 10 carbon atoms, preferably a perfluoroalkyl group having 6 to 8 carbon atoms, and Or a branched chain.
本発明化合物の特性である撥水、撥油性、非粘着性な
どはこのペルフルオロアルキル基によつて発揮されるも
のである。炭素数が４未満であると撥水、撥油性、など
が十分ではなく、また10を越えると、それ以下の場合と
比較して特性の大きな変化は認められない。The properties of the compound of the present invention, such as water repellency, oil repellency, and non-adhesion, are exhibited by the perfluoroalkyl group. If the number of carbon atoms is less than 4, water repellency and oil repellency are not sufficient, and if it exceeds 10, no significant change in characteristics is observed as compared with the case of less than 4.
また、エーテル結合は、その柔軟性より得られたウレ
タン化合物の柔軟性や加工性を高める効果をもたらす。In addition, the ether bond has an effect of improving the flexibility and processability of the urethane compound obtained from the flexibility.
さらに、２個の水酸基は、２官能型のモノマーとして
作用し、ジイソシアネートとの反応によつて高分子量の
化合物を得るために必要不可欠のものである。Furthermore, the two hydroxyl groups act as bifunctional monomers and are essential for obtaining high molecular weight compounds by reaction with diisocyanate.
これによつて、高分子量の重合物が得られ、樹脂の硬
度、耐薬品性、耐熱性、溶融温度等を高める効果を持
つ。As a result, a polymer having a high molecular weight can be obtained, which has the effect of increasing the hardness, chemical resistance, heat resistance, melting temperature and the like of the resin.
本発明化合物の原料である一般式（１）で表される化
合物は、対応する含フツ素エポキシドの開環反応によつ
て容易に得られる。The compound represented by the general formula (1) as a raw material of the compound of the present invention can be easily obtained by a ring-opening reaction of the corresponding fluorine-containing epoxide.
また、本発明化合物の製造方法において、ジイソシア
ネートは直鎖、分岐鎖のいずれであつてもよく、また脂
肪族、芳香族のいずれであつてもよいが、一般的な例と
して、ヘキサメチレンジイソシアネート（HDI）、2,4−
トリレンジイソシアネート（2,4−TDI）、メチレンビス
（４−フエニルイソシアネート）（MDI）、キシリレン
ジイソシアネート（XDI）、３−イソシアネートメチル
−3,5,5−トリメチルシクロヘキシルイソシアネート（I
PDI）等があげられる。In the method for producing the compound of the present invention, the diisocyanate may be either linear or branched, and may be aliphatic or aromatic. As a general example, hexamethylene diisocyanate ( HDI), 2,4-
Tolylene diisocyanate (2,4-TDI), methylene bis (4-phenyl isocyanate) (MDI), xylylene diisocyanate (XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (I
PDI).
このジイソシアネートの使用量は、特に限定されない
が、一般式（１）で示される含フツ素ジオールに対して
0.5〜1.5（モル比）の間で用いられる。The amount of the diisocyanate is not particularly limited, but is based on the fluorine-containing diol represented by the general formula (1).
It is used between 0.5 and 1.5 (molar ratio).
ここで、ジイソシアネートの使用量が0.5付近である
と、含フツ素ジオール１分子に対してジイソシアネート
２分子、また1.5付近であると、ジイソシアネート２分
子に対して含フツ素ジオール３分子が反応したテロマー
が得られる。When the amount of diisocyanate used is around 0.5, two molecules of diisocyanate are reacted with one molecule of fluorine-containing diol, and when the amount is around 1.5, three molecules of fluorine-containing diol are reacted with two molecules of diisocyanate. Is obtained.
一方、ジイソシアネートの使用量が１付近であると、
含フツ素ジオール１分子に対してジイソシアネートも１
分子反応した高分子化合物が得られる。また、反応温度
は室温から含フツ素ジオールおよびジイソシアネートの
沸点まで変化できるが、好ましくは40℃〜120℃の間
で、無溶媒、または必要に応じて適当な溶媒を用いて行
われる。On the other hand, when the use amount of the diisocyanate is around 1,
One diisocyanate per molecule of fluorine-containing diol
A polymer compound having undergone a molecular reaction is obtained. The reaction temperature can vary from room temperature to the boiling point of the fluorine-containing diol and diisocyanate, but is preferably between 40 ° C. and 120 ° C. in the absence of a solvent or, if necessary, using a suitable solvent.
このようにして得られる本発明化合物は、含フツ素化
合物の特徴として、上記の撥水、撥油性の他に、低屈折
率、気体の選択的透過性などの諸特性も併せ持つ。The compound of the present invention thus obtained has characteristics such as low refraction index and selective gas permeability in addition to the water repellency and oil repellency as characteristics of the fluorine-containing compound.
次に、本発明を実施例をもつて具体的に説明するが、
以下の実施例は本発明の範囲を限定するものではない。Next, the present invention will be described specifically with examples,
The following examples do not limit the scope of the invention.
実施例１ 十分にN2パージをした、機械撹拌装置、温度計、滴下
斗、還流器を備えた300ml三口フラスコに、含フツ素
ジオール を入れ、N2雰囲気下80℃でヘキサメチレレンジイソシア
ネート16.8g（0.10mol）を30分で滴下し、そのままの状
態で８時間撹拌した。撹拌終了後、空気中でさらに６時
間そのままの温度で撹拌をして含フツ素ポリウレタンを
得た。Example 1 A fluorine-containing diol was placed in a 300 ml three-necked flask equipped with a mechanical stirring apparatus, a thermometer, a dropping funnel, and a reflux condenser sufficiently purged with N 2. Was added thereto, and 16.8 g (0.10 mol) of hexamethylylene diisocyanate was added dropwise at 80 ° C. for 30 minutes under an N 2 atmosphere, and the mixture was stirred for 8 hours as it was. After completion of the stirring, the mixture was further stirred at the same temperature for 6 hours in the air to obtain a fluorine-containing polyurethane.
m.p.68℃ IR（neat、cm-1） 3330,2930,2860,1710,1580,1300〜1150 実施例２ 機械撹拌装置、温度計、滴下斗、還流器を備えた50
0ml三口フラスコに、 を入れ、N2雰囲気下60℃で、滴下斗よりキシリレンジ
イソシアネート28.2g（0.15mol）、を30分で滴下した。
滴下終了後そのままの温度で６時間撹拌して含フツ素テ
ロマーを得た。mp 68 ° C IR (neat, cm -1 ) 3330,2930,2860,1710,1580,1300-1150 Example 2 50 equipped with a mechanical stirrer, thermometer, dropping funnel and reflux condenser
In a 0 ml three-necked flask, Was added, and 28.2 g (0.15 mol) of xylylene diisocyanate was added dropwise from the dropping funnel at 60 ° C. under N 2 atmosphere in 30 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 6 hours to obtain a fluorine-containing telomer.
（発明の効果） 本発明は上記の構成をとることによつて、次の効果を
示す。(Effect of the Invention) The present invention has the following effects by adopting the above configuration.
（１） 得られた含フツ素ウレタン化合物は高められた
撥水性、撥油性、非粘着性を有する。(1) The obtained fluorine-containing urethane compound has enhanced water repellency, oil repellency, and non-adhesion.
（２） この含フツ素ウレタン化合物よりなる樹脂は向
上した硬度、耐薬品性、耐熱性を有する。(2) The resin comprising the fluorine-containing urethane compound has improved hardness, chemical resistance and heat resistance.
Claims (5)
ｎは１または２の整数）で表される含フッ素ジオールを
ジイソシアネートと反応させることからなり、ジオール
反応成分が含フッ素ジオールのみからなる、含フッ素ウ
レタン化合物の製造法。(1) General formula (Wherein, R f is a perfluoroalkyl group having 4 to 10 carbon atoms,
n is an integer of 1 or 2). A process for producing a fluorine-containing urethane compound, comprising reacting a fluorine-containing diol represented by the formula (1) or (2) with a diisocyanate, wherein the diol reaction component comprises only a fluorine-containing diol.
８である請求項１に記載の含フッ素ウレタン化合物の製
造法。2. The perfluoroalkyl group Rf has 6 to 6 carbon atoms.
The method for producing a fluorine-containing urethane compound according to claim 1, wherein
びジイソシアネートの沸点までの間である請求項１また
は２に記載の含フッ素ウレタン化合物の製造法。3. The process for producing a fluorine-containing urethane compound according to claim 1, wherein the reaction temperature is between room temperature and the boiling point of the fluorine-containing diol and diisocyanate.
記載の含フッ素ウレタン化合物の製造法。4. The method for producing a fluorine-containing urethane compound according to claim 3, wherein the reaction temperature is 40 ° C. to 120 ° C.
ールに対して0.5〜1.5（モル比）である請求項１ないし
４のいずれか１項に記載の含フッ素ウレタン化合物の製
造法。5. The process for producing a fluorine-containing urethane compound according to claim 1, wherein the amount of the diisocyanate used is 0.5 to 1.5 (molar ratio) with respect to the fluorine-containing diol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1081053A JP2699539B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing fluorine-containing urethane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1081053A JP2699539B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing fluorine-containing urethane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02258822A JPH02258822A (en) | 1990-10-19 |
| JP2699539B2 true JP2699539B2 (en) | 1998-01-19 |
Family
ID=13735672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1081053A Expired - Fee Related JP2699539B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing fluorine-containing urethane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2699539B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7258925B2 (en) | 2003-07-11 | 2007-08-21 | E.I. Du Pont De Nemours And Company | Fluorochemical finishes for paint applicators |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046944A (en) * | 1976-04-06 | 1977-09-06 | Ciba-Geigy Corporation | Fluorinated condensation polymers and their use as soil release agents |
| JPS61252220A (en) * | 1985-04-30 | 1986-11-10 | Dainippon Ink & Chem Inc | Polyurethane resin |
| JPH0674312B2 (en) * | 1987-03-24 | 1994-09-21 | アキレス株式会社 | Polyurethane resin manufacturing method |
| JP2631501B2 (en) * | 1988-03-23 | 1997-07-16 | 日本化薬株式会社 | Resin composition and cladding material for optical fiber |
-
1989
- 1989-03-31 JP JP1081053A patent/JP2699539B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02258822A (en) | 1990-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3268864B2 (en) | Fluorinated polyurethane and fluorinated polyurethane-urea and methods for their production | |
| US2911390A (en) | Fluorinated polyurethane resins | |
| US6448368B1 (en) | Polymers and prepolymers formed from mono-substituted fluorinated oxetane monomers | |
| KR100420261B1 (en) | Coatings based on fluoropolyethers | |
| EP0192190B1 (en) | Fluorinated polyurethanes containing polyoxyperfluoroalkylene blocks | |
| KR100311606B1 (en) | Fluoropolymers containing perfluoropolyoxyalkylene sequences and having the properties of thermoplastic and elastomeric polymers | |
| KR100345093B1 (en) | Fluoropolyether Substrate Coating | |
| CA2064986C (en) | High performance polyurethane coating compositions and processes for making same | |
| JPH0772227B2 (en) | Fluorinated polymer | |
| JP2003524684A5 (en) | ||
| JP2003524684A (en) | Amorphous polyether glycol based on bis-substituted oxetane monomer | |
| JP2019218536A (en) | Polyol for crosslinkable polyurethane resin composition, and crosslinkable polyurethane resin | |
| JP3098015B2 (en) | Fluorinated polyurethanes containing polyoxyperfluoroalkylene blocks and having improved mechanical properties | |
| US5494990A (en) | Thermoplastic polyurethane resin having broad rubbery-state region and process for producing the same | |
| JPH0192277A (en) | Fluorinated polyisocyanate applicable as paint component | |
| JP3448694B2 (en) | Polyurethane having a fluorene skeleton | |
| JPH0375557B2 (en) | ||
| JP2699539B2 (en) | Method for producing fluorine-containing urethane compound | |
| JP2699538B2 (en) | Method for producing fluorine-containing urethane compound | |
| US3642705A (en) | Fluorine-containing polyurethane rubbers | |
| EP1728788B1 (en) | Fluorine-containing amide compound and method for preparing the same | |
| CA1263494A (en) | Polyester polyols, their manufacture and use in polyurethane production | |
| CA2114577A1 (en) | Di- and polyamino compounds for use in the preparation of polyurethanes | |
| CN118652406A (en) | Preparation of Perfluoropolyether Modified Long Fluorinated Side Chain Polyurethane Acrylate | |
| CN108250406B (en) | Polyurethane containing soft segment, polyvalent isocyanate, urethane prepolymer and polyurethane elastomer and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |