JP2699538B2 - Method for producing fluorine-containing urethane compound - Google Patents
Method for producing fluorine-containing urethane compoundInfo
- Publication number
- JP2699538B2 JP2699538B2 JP1081052A JP8105289A JP2699538B2 JP 2699538 B2 JP2699538 B2 JP 2699538B2 JP 1081052 A JP1081052 A JP 1081052A JP 8105289 A JP8105289 A JP 8105289A JP 2699538 B2 JP2699538 B2 JP 2699538B2
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052731 fluorine Inorganic materials 0.000 title claims description 26
- 239000011737 fluorine Substances 0.000 title claims description 26
- -1 urethane compound Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 150000002605 large molecules Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 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
- 238000003756 stirring Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
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
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
- C08G18/3861—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur containing sulfonamide and/or sulfonylhydrazide groups
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、
ペル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54−7400
0号公報）。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 remedy these shortcomings,
Urethane compounds having a perfluoroalkyl group have been studied (JP-A-53-112855, JP-A-54-7400).
No. 0).
このペル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、また撥水性、撥油性、
硬度などがまだ十分でないといつた欠点があつた。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。The urethane compound having a perfluoroalkyl group is classified into a low molecular weight compound and a high molecular weight compound. The low molecular weight compound has a large amount of a reaction product between a fluorine-containing monoalcohol and an isocyanate, and thus has a dimer, It is difficult to obtain telomers such as dimers, many of low molecular weight compounds, therefore low melting temperature, water repellency, oil repellency,
There was a drawback that the hardness was not enough yet. 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、分子中にスルホンアミド結合を有する
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。(Objects of the Invention) The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a reaction product of a fluorine-containing diol having a sulfonamide bond in a molecule and a diisocyanate has an object of the present invention. The present invention has been found to be suitable for 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、そ
れに結合したスルホンアミド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、
R1は炭素数１〜５のアルキル基）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 perfluoroalkyl group having 4 to 10 carbon atoms and a sulfonamide bond bonded thereto in a molecule, and at least one urethane bond per polymer segment. A fluorine-containing urethane compound having the general formula (2) (Wherein R f is a perfluoroalkyl group having 4 to 10 carbon atoms,
R 1 is an alkyl group having 1 to 5 carbon atoms), and a method for producing a fluorine-containing urethane compound, characterized by reacting a diisocyanate with a fluorine-containing diol.
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性、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未満では撥水性、撥油性、硬度
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みられない。一方、
R1は炭素数が１〜５のアルキル基である。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, oil repellency, hardness and the like are not sufficient, and if it exceeds 10, no significant change in characteristics is observed as compared with the case of less than 4. on the other hand,
R 1 is an alkyl group having 1 to 5 carbon atoms.
また、スルホンアミド結合は、熱的、化学的安定性、
および分子の剛直性よりペルフルオロアルキル基の配向
をもたらし、撥水性、撥油性、非粘着性をより高める効
果をもたらすとともに、得られたウレタン化合物の硬度
および、溶融温度を高める効果を持ち、窒素原子に結合
しているアルキル基は、重合時の溶媒との相溶性を高め
る。Also, the sulfonamide bond has thermal, chemical stability,
And has the effect of increasing the water repellency, oil repellency, and non-adhesiveness, and has the effect of increasing the hardness and melting temperature of the resulting urethane compound. The alkyl group bonded to the compound increases the compatibility with the solvent during the polymerization.
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、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, a telomer obtained by reacting two molecules of diisocyanate with one molecule of fluorine-containing diol and near 1.5 is obtained by reacting three molecules of fluorine-containing diol with two molecules of diisocyanate. Can be
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、上記の撥水性、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 obtained in this way has, as features of the fluorine-containing compound, various properties such as a low refractive index and selective gas permeability in addition to the above-described water repellency and oil repellency.
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) Fluorine-containing diol was placed in a 300 ml three-necked flask equipped with a mechanical stirrer, 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 hexamethylene diisocyanate was added dropwise at 80 ° C. over 30 minutes under a 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.112℃ IR（neat、cm-1） 3330,2930,2960,1710,1580,1400,1300〜1150 （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。撹
拌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。mp112 ° C IR (neat, cm -1 ) 3330,2930,2960,1710,1580,1400,1300-1150 (Example 2) 50 equipped with a mechanical stirrer, thermometer, dropping funnel and reflux condenser
In a 0 ml three-necked flask, And 28.2 g (0.15 mol) of xylylene diisocyanate was added dropwise from the dropping funnel over 30 minutes at 60 ° C. under N 2 atmosphere. After the completion of the stirring, 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、溶融温度を有する。(2) The resin comprising the fluorine-containing urethane compound has improved hardness, chemical resistance, heat resistance, and melting temperature.
Claims (5)
R1は炭素数１〜５のアルキル基）で表される含フッ素ジ
オールにジイソシアネートを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方法。(1) General formula (Wherein, R f is a perfluoroalkyl group having 4 to 10 carbon atoms,
R 1 is a reaction of a diisocyanate with a fluorinated diol represented by an alkyl group having 1 to 5 carbon atoms,
A method for producing a fluorinated urethane compound in which the diol reaction component comprises only a fluorinated 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
造方法。2. A perfluoroalkyl group having a carbon number of R f NO of 6 to 6.
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方法。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方法。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
造方法。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 |
|---|---|---|---|
| JP1081052A JP2699538B2 (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 |
|---|---|---|---|
| JP1081052A JP2699538B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing fluorine-containing urethane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02258821A JPH02258821A (en) | 1990-10-19 |
| JP2699538B2 true JP2699538B2 (en) | 1998-01-19 |
Family
ID=13735644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1081052A Expired - Fee Related JP2699538B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing fluorine-containing urethane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2699538B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114578459A (en) * | 2022-04-18 | 2022-06-03 | 安徽潜隆机电科技有限公司 | Corrosion-resistant elastic lens for gas mask |
| CN115058224B (en) * | 2022-06-27 | 2023-09-22 | 浙江华峰合成树脂有限公司 | Reactive polyurethane hot melt adhesive |
Family Cites Families (3)
| 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 |
-
1989
- 1989-03-31 JP JP1081052A patent/JP2699538B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02258821A (en) | 1990-10-19 |
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