JPS63225347A - Fluorine-containing azide compound - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing azide compound containing a partially or totally fluorinated alkyl chain polyether chain as a fundamental skeleton and having structure wherein azide group exists through a nonfluorine functional group. USE:Useful as a stainproofing agent, water-repellent and oil-repellent treatment, lubricant, releasant and synthetic intermediate. Having surface stabilizing action on the surface of solid. PREPARATION:A compound shown by formula (CnF2n+1) is reacted with a compound shown by formula E-(CmH2m)-D to form partial structure A. The partial structure A is reacted with a compound shown by formula G-N3 to form a partial structure B, which is bonded to give the titled compound. In the formula, D is X, -COX or -CO2R (X is halogen; R is H or alkyl); E is -CH=CH2-OH; G is -LNH2 (L is aromatic group); n is 3-20; m is 0-30; A is functional group such as -CH2CH2- or -CO2-; B is functional group such as -CONHL-.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel fluorine-containing azide compound, and the compound of the present invention can be used, for example, in polymers.

[Conventional technology]

The compounds according to the present invention are fluorine-containing azides having a basic skeleton of a fluoroalkyl chain or a fluoropolyether chain, and the following publications are representative examples of the prior art.

Japanese Patent Publication No. 60-34924. US Pat. No. 3,250,808, US Pat. No. 3,810,874, etc. disclose perfluoropolyethers.

However, none of the above publications describes a compound having an azide group in its molecular structure.

Also, Journal of Chemical Society
C: (1970) p. 1017 (J, C, S (C)
, 1017 (1970) is CHF
N 3 (However, X is -F, -CQ.

-I or -CFs) are described.

US Pat. No. 4,474,700, Journal of Organic Chemistry, 51. (1986) p. 332 (
JOC, Presentation, 332 (1986)) discloses fluoroalkyl azides, all of which have terminals of -CFY CF, N5 (Y is CM, F, -Br
, oRr (Rr is a perfluoroalkyl group having 1 to 10 carbon atoms, etc.)].

[Problem that the invention seeks to solve]

Azides having a fluorinated alkyl chain or a polyether chain as a basic skeleton are hardly known except for a few examples typified by the above-mentioned prior art.

An object of the present invention is to provide novel fluorine-containing azides.

[Means for solving problems]

The above object is a fluorine-containing azide compound characterized by having a structure in which the basic skeleton is a partially or entirely fluorinated alkyl chain or polyether chain, and an azide group is present via a non-fluorine functional group. This is achieved by Therefore, it is clearly a new metal compound with a structure different from the conventional compounds mentioned above.

Examples of the fluorine-containing azide according to the present invention include compounds represented by formulas (1) to (4).

Formula (1): (CnFzn+t+(Aei(CmHzm+
(B+JN3 formula (2): N a (-B+ J (
Cm 82 m+ (Aet (Cn F 2 J (
Ae-i(Cm82 m+ (B+a N 3 CF3 CF3 Formula (4): N 34B+J (Cm82m+(Ae
t (CF 20 (Ct, F2t, ○) P (CF 2
0+qCF J(Aet(CmH2m+(B+JN3) (However, A is -C:H2CH2+.

A functional group represented by -CHCH2-1 or -〇〇2-, B is a functional group represented by -〇〇NHL- (L is an aromatic group), n is an integer from 3 to 20, and m is an integer from 0 to An integer up to 30, m + j is 0 or 1, respectively, and f <
i + j≦2, r is an integer from 1 to 100, t is 2 or 3, and the molecule may contain t of 2 and 3 at the same time <-P? Each q is an integer from 1 to 100. ) As the value of P+q, P/'T is 0.2/1 to 5
It is preferably in the range of /1.

(CnF2n+x+ and + in the above formulas (1) and (2)
Fluorocarbon segment represented by Cn F z m+ and + Cm 82 in formulas (1) to (4)
The hydro-bond segment represented by m+ includes not only linear segments but also those with a branched structure. The perfluoropolyether chain in the above formula (3) may include a -CF20- segment.

The perfluoropolyether chain in the above formula (4) may include a -C3F,O- segment and a -C,F40- segment.

In the above formula, the aromatic group of L is a phenylene group, a halogenophenylene group, or a toluylene group.

Examples include xylylene group, naphthylene group, and anthracenylene group.

The compounds of formulas (1) to (4) above are the target substances of the present invention, but they can be synthesized using, for example, the compounds shown in groups (1) to (■) as raw materials.

Group (1) (CnF2n+x+D o+cnF2n+D CF3CF3D-(CF20(Ct, F x t, 0) p(CF
20) -1cF JD group (II) E+CmHsm+D (ii) group (m
) G-N, (blood) [However, m, n, r, t, p, and q represent the same meanings as above, and D and E are functional groups that can react with each other to produce the above-mentioned partial structure A. The groups G are functional groups that can react with each other to produce the above-mentioned partial structure B. ] In the above formula, the functional groups E and G can be exemplified by the following, respectively.

As D, X (X is a halogen atom, CD, Br.

I16) , -〇〇X, -Co As 2RE, -
CH=CH2, -0H G is -LNH2 (L has the same meaning as above, R is a hydrogen atom or an alkyl group), and the like.

D, E, and G not only directly produce structures A and B by reaction, but also react with each other and form a second structure.

Structures A and B may be formed by a third reaction, which will be described later.

The compounds of formulas (1) to (4) can be obtained by forming a partial structure A from a compound (i L Step of forming structure B, compound (i/), (iiL)
Synthesis is possible by selecting one or more of the steps for forming the partial structure B.

More specifically, first-order processes (a) to (C) can be exemplified.

Process (a) Compound (i) Ten compound (ii) ↓ (forms partial structure A and joins) ↓ Ten compound (iii) ↓ (forms partial structure B and joins) Product process (b) Compound (+) ten Compound (iii) ↓ (forming partial structure B and joining) Product process (e) Compound (i) Ten compounds (ii) ↓ (forming partial structure A and joining) ↓ (azidation) Product compound (i) When using only the reaction between (ii) and (ii), it is necessary to further azidate and introduce an azide group.

The functional groups (D, E, G) involved in the reaction of compounds (i) to (iii) in the above process and the generated partial structures (A, B) are illustrated in Table 1.

A fluorine-based solvent is used as a reaction solvent in each reaction.

A hydrocarbon solvent or a mixed solvent of both may be used.

Examples of the fluorine-based solvent include fluorocarbons and fluorochlorocarbons, and specific examples include trichlorotrifluoroethane, perfluoro-2-butyltetrahydrofuran, and perfluorohebutane.

Examples of hydrocarbon solvents include ether and ketone.

Examples include hydrocarbons and alcohols, and specific examples include diethyl ether, acetone, benzene, hexane, and methanol.

In the reaction, in addition to using the above-mentioned solvents alone or as a mixed solvent, there is also a method in which the reactants are separately dissolved in a fluorine-based solvent and a hydrocarbon-based solvent and reacted in the form of a solution.

Compounds (1) to (3i) react approximately stoichiometrically, although there is some variation depending on the drying state, stirring state, etc. of the reaction system.

Therefore, the charging ratio of each compound is from 0.5 to 0.5 in terms of equivalent ratio.
A range of 2 times is preferable from the viewpoint of removing unreacted substances.

As a method for purifying the reaction product, well-known methods such as extraction, distillation, and liquid chromatography can be applied.

In addition, as compounds of the present invention, Table 52 Table 7 Tables 9 to 1
Examples include the fluorine-containing azide described in Example 1.

Although not all structures are specified here, compounds with different molecular weights, compounds with a branched basic skeleton,
It goes without saying that a compound having a perfluoroalkyl chain containing an ether bond at any position can also be synthesized in the same manner as described above.

The compound of the present invention can be used to convert an azide group (-N3) introduced into the molecular structure into nitrene (nitrogen biradical; -N.) by heat or photolysis, so it can be used in many organic materials including polymers. Can form chemical bonds with compounds, etc.

The compound of the present invention can be applied to various uses due to the reactivity of the azide group and the molecular function of the basic skeleton containing fluorine.

It can be used as a lubricant, etc.

〔Example〕

In the examples of the present invention, the iodides, acid chlorides, and carboxylic acid esters used as raw materials are as follows.

Next, it was synthesized by the steps outlined below.

(However, RF is a perfluoroalkyl chain or a perfluoropolyether chain, and R is an alkyl group.) Diiodide is prepared from dicarboxylic acid in the same manner.

Diacid chlorides and dicarboxylic acid esters were synthesized.

Next, a typical synthesis example will be shown.

Synthesis Example 1-1 (Synthesis of polyhexafluoropropylene oxide-ω-acid chloride) Polyhexafluoropropylene oxide acid (DuPont product name Krytox 157 F S/L; average molecular weight 2500) 30 g to 1,1 .2-Trichlorotrifluoroethane (Dupont trade name Freon TF,
(hereinafter abbreviated as Freon) was dissolved in 100 mQ. After drying the above solution with magnesium sulfate, 10 g of thionyl chloride was added and refluxed for 2 hours.

After the reaction was completed, the solvent and unreacted thionyl chloride were distilled off to obtain the acid chloride (1).

In the infrared spectrum of this substance, carbonyl group absorption was observed at 1790c''''1.

Synthesis Example 1-2 (Perfluoropolyether-α.

Synthesis of ω-diacid chloride) Perfluoropolyether-α, ω instead of polyhexafluoropropylene oxide acid in Synthesis Example 1-1
-Diacid (Monteflores product name Fomblin Z)
-DIAC; average molecular weight 2000) using 20g, HO2C(CF20) P (CF2CF20)
9CF x CO2H Following the same procedure, α in (2)
, ω-diacid chloride was obtained.

CQOCCCCF20)P(CF2CFso)qCOCQ
(2) In the infrared spectrum, 1790c
In 1, the absorption of carbonyl group is Il! It was measured.

Synthesis Example 2-1 (Synthesis of methyl polyhexafluoropropylene oxide-ω-acid) After 1 reaction in which 10 g of acid chloride (1) was dissolved in 50 mm of dry Freon, and 50 ml of methanol was gradually added while stirring. The solvent was distilled off to obtain methyl ester (7).

In the infrared spectrum, there is an absorption attributable to the carboxyl group at 1780c■-1, and in the 'H-NMR spectrum, there is an absorption attributable to δ
Absorption by -CH and protons was observed at =3.7 ppm.

Synthesis example 3 (polyhexafluoropropylene oxide-ω
- Synthesis of Iodide) 125 g of polyhexafluoropropylene oxide acid (average molecular weight 2500) was dissolved in 200 mQ of Freon, 12.5 g of silver oxide (1) was added, and the mixture was stirred for about 24 hours. Next, unreacted silver oxide was separated into 7 parts,
The solvent was distilled off from the Z solution to obtain a silver salt.

After mixing 52 g of the above silver salt and 6 g of iodine, the mixture was placed in a flask equipped with a dry nitrogen gas inlet, a calcium chloride tube, and a cooling tube, and refluxed at 140 to 150° C. for about 7 hours.

After cooling the above product to room temperature, it was made into a Freon solution, and after separating three portions of silver iodide, the solvent was distilled off to obtain iodide (13).

In the infrared spectrum, the absorption of carbonyl groups disappeared.

In 19F-NMR, absorption attributable to the CFI structure was observed at 78.9 ppm (based on CsFg).

According to the methods described in Synthesis Examples 1 to 3 above, acid chlorides, carboxylic acid esters, and iodides synthesized from perfluoropolyether acids and perfluorocarboxylic acids were used as raw materials.

Next, the present invention will be specifically explained by showing examples and application examples.

A fluorine-containing azide of the type Rr CONHLN a (Rr = L is the same as above) was first synthesized by the steps schematically shown.

M or RrCO2R*/'ma) (HLN3 or -1-----→ R(CONH
The above process was similarly applied to LNaRrCOCfl dicarboxylic acid ester and diacid chloride. The successful flow of the above process is shown below.

Example 1 25 g of the acid chloride (1) of Synthesis Example 1 above was added to a flechion-diethyl ether mixed solvent (volume [1:1) 2
00rnQ, and 1.6 g of p-azidoaniline was added. After stirring at room temperature for 30 minutes, the solvent was distilled off to obtain the next fluorine-containing azide (14).

The yield was 17 g (yield 68%). In the infrared spectrum, NH at 3300-2400 cm-1.

Absorption by CH, absorption by -N3 at 2110 cm+-', absorption by C=0 at 1660 cm-1, 1400
Absorption due to CF was observed at −1000 cm''. In the UV spectrum, 1 m a X + in methanol = 2
It was 59 nm.

Example 2 25 g CF of polyhexafluoropropylene oxide-ω-ethyl acid (8) synthesized according to Synthesis Example 1,
C.F.

was dissolved in perfluoro-2-butyltetrahydrofuranz 100 m Q, and p-azidoaniline 2
50 mQ of an acetone solution containing g was gradually added.

After refluxing the above mixture at about 40° C. for 1 hour, the solvent was distilled off to obtain azide (14). Yield: 21g (yield: 84%)
), and when the infrared spectrum and ultraviolet spectrum were measured, the same results as in Example 1 were obtained.

Examples 3 to 10° Acid chloride following a procedure similar to Example 1.2.

Table 2 shows the structures of reactants and products synthesized by changing the types of carboxylic acid ester and aromatic azide.
The infrared and NMR analysis results of the product are shown in Table 6.

These analytical results support the above structure.

Table 2 Table 3 Ry CH2CHz (CTrIH2m)CON HL
The fluorine-containing azide compound is N 3 (RF? m v L is the same as above).

Next, it was synthesized by the steps outlined below.

Rr I +CH2=CH(CmH2m)CoxH
OH → Rr CH= CH (Cm 82 m) GO2K connection → Rr CH=CH (CmH2m) Co 2
H billion medium HCQ) □□□ medium Pd-C) 0CQ2 →Rr CH2CH2 (Cm82m) COCQ then Rr CHSI CH2 (Cm Hz m) COCQO
H −→ R(CH2CH2(Cm82 m)Co2
RNH2LN.

1 → RrCHzCHz (CmHzm) CONHL
N3 or Rr CHz CH2(CmH2m)COCQH,NL
N3 Issun RrCH2cH (CmHzm) CONHLN
The above process was similarly applied to tridiiodide.

The successful flow of the above process is shown below.

Example 11゜ 50 g perfluoro-n-hebutyl iodide.

18 g of 10-landecylenilic acid and 1.6 g of azoisobutyronitrile (AIBN) were refluxed in nitrogen at 70 to 80° C. for about 5 hours to obtain the fifth compound.

F(CF2)7GHzcH(CHz)scOs+H 68g of the above compound and 112g of potassium hydroxide were dissolved in 1000 mQ of ethanol and stirred for about 24 hours.
8 g was dissolved in 300 mΩ of ethanol and hydrogenated using 6 g of 5% palladium carbon at room temperature and pressure to obtain a primary compound.

F(CF ri7(CH2) CO, H 12 g of thionyl chloride was added to 200 mg of a Freon solution containing 27 g of the above compound, and after refluxing for about 30 minutes, unreacted thionyl chloride and Freon were distilled off to obtain the following compound. .

䋋F (CF g)7(CH2)IOCOCQ
(27) 20 g of the above compound was dissolved in Freon 100mα, methanol LOOm, Q was added, and the solvent was distilled off to obtain the following compound.

F(CFz)7(CHz)10cOzcH3 15g of the above compound was dissolved in Freon 100mQ, and a diethyl ether solution containing 3.5g of P-azidoaniline was added to 100%
m Q was added. After stirring at room temperature for 1 hour, the solvent was distilled off to obtain the following azide.

F (CF2)? (CHz)iocONHON3
(23) The yield was 16 g (yield 92%; based on F(CFz)t(CHz) trout COz CHa).

In the infrared spectrum of the above azide (23), 3300-
Absorption by NH and CH on 2400c sheet-1.

Absorption due to N3 was observed at 2110 cm-1, absorption due to C=0 at 1660 cm-1, and absorption due to CF and CH at 1400-1000 cm''1. In the NMR spectrum, the phenylene skeleton (-□-
) was wits protons. Also.

The elemental analysis results are shown below.

The above analysis results support the above structure.

Example 12 22 g of the acid chloride (22) described in Example 11 and p-
4.5 g of azidoaniline was dissolved in a freon-diethyl ether mixed solvent (volume 1:1).

After stirring at room temperature for 30 minutes, the solvent was distilled off to obtain the azide (23) described in the example.

The infrared spectrum and NMR spectrum gave the same results as in Example (23).

Elemental analysis values are C: 43.10%, H: 3.75%, F
:42.51%.

The structure of the product was confirmed from the above analysis results.

Examples 13 to 16 According to the method described in Example 11, R(CH
g CHx (Cm 82m) COCQ type and C
Q OC(Cm H2m) CH2CH2Rr CH
2CHs (CmH) Acid chloride of the COCa type.

RrCH1CH2 (CHH2Tn) COgR type and
RO2C(CTnH2Tn) CH2CH2RrCHx
CH*(CmH*m)COaR type ester was synthesized.

Example 1 from esters, acid chlorides, and aromatic azides
Table 7 shows the structure of the fluorine-containing azide synthesized according to the method in 1.12.

Further, Table 8 shows the results of infrared and NMR analysis of the fluorine-containing azide.

These analytical results support the above structure.

R,CO2(CmH2m)N3 type fluorine-containing azides were synthesized by the following reaction.

The above reaction was similarly applied to Rr COCQ + HO(Cm 82 m)N 3-1--→RrC○2 (Cm H2m)N 3 diacid chloride.

The successful flow of the above reaction is shown below.

Example 17 Polyhexafluoropropylene oxide-ω-acid chloride (1) 1.7 g of azide ethanol was added to 100 mQ of a Freon solution containing 25 g, and the mixture was stirred at room temperature for about 30 minutes. After the reaction was completed, unreacted azide ethanol and the solvent were distilled off to obtain the next azide.

The yield of CF3 0F3 was 24 g (yield 96%). In the infrared spectrum, absorption due to diCH at 2800 to 3000 cm-' and absorption due to N3 at 2112 cm-' were observed.

In the NMR spectrum, C
COz in H2N3 proton, δ = 4.1-4.6PPm
CHz-protons were measured wt.

The above analysis results support the above structure.

Examples 18-22゜Example 1 using the acid chloride and azide alcohol shown in Table 2
Table 9 shows fluorine-containing azides synthesized in the same manner as in Example 7.

In the infrared spectra of these azides, both 280
Absorption by CH at 0-3000 cm-'.

Absorption due to N3 was observed at 2112 cm-'.

In both NMR spectra, δ=2.8-3.0p
CHN and protons were observed at pm, and GO2CH and protons were observed at δ=4.1 to 4.6 ppm.

The above analysis results support the above structure.

The RrC82CH*(CmH2m)Na (Rrlm is the same as above) type fluorine-containing azide was synthesized by the steps outlined below.

Rr I + CH2=CH (CmHx m)OH Heated in nitrogen I OH → RrCH=CH (CTnH2,yl)OH
Hydrogenation sCQ aN3 Issun RrCH2CH2(CmH2m)N 3
The above process was similarly applied to diiodide.

The successful flow of the above process is shown below.

Example 23゜ 55 g of perfluoro-n-octyl iodide.

17 g of 10-landecylenyl-1-ol and 1.6 g of azoisobutyronitrile (AIBN) in nitrogen at 70 g.
Reflux at ~80°C for about 5 hours.

The following compound was obtained.

F(CF2)B CHz CH(CHz)s OH 36g of the above compound and 28g of potassium hydroxide were mixed with 33g of ethanol
00mQ and stirred for about 24 hours.

F(CFz)aCH=CH(CH2)90H 24 g of the above compound was dissolved in 300 mQ of ethanol and hydrogenated using 4 g of 5% palladium carbon at room temperature and normal pressure to obtain the following compound.

F(CFz)scH*cHz(CmHzm)OH After drying 350 mQ of diethyl ether solution containing 12 g of the above product over molecular sieve 3A.

5 m fl of triethylamine (EtaN) was added and the mixture was cooled with water. methanesulfonyl chloride (MsCQ) at 0°C.
) was added dropwise and stirred for 1.5 hours. The above solvent was distilled off to obtain the following compound.

F(CF+1)IICH2CH2(CHz)sOMg
7 g of the above product + iodide was distilled off in 200 mQ of acetone to obtain a reddish-brown shell. This is diethyl ether 1
A solution of 50mff1 was prepared, an aqueous sodium thiosulfate solution was added thereto, the mixture was shaken, and the ether layer was washed with water.

After drying, the solvent was distilled off to obtain the following compound.

F(CF*)a CHx CH2(CH2) s I
Dissolve 3.5 g of the above compound in 40 mQ of acetone, and add 10 ml of an aqueous solution containing 0.5 g of sodium azide to the above solution.
2 was added and stirred for 8 hours. After distilling off the solvent, a 20 mQ aqueous solution was prepared, and the target component was extracted with diethyl ether.

After drying the ether layer, the solvent was distilled off to obtain a primary azide.

F(CFz)e(CHz)1tN　3 Yield: 2.8g (yield 60%; F(CFz)e(CH2)110H standard).

In the infrared spectrum, C at 2800-3000 cm-'
Absorption due to H, absorption due to N3 at 2112cya-'' was measured. In the NMR spectrum, δ = 1.lpp
10H2-proton in m, 2.9 ppm (t, ripi
et) to -〇)(, N3 proton, 3.9 ppm (tr
iple 7), CF2CH2 protons were observed.

The above analysis results support the above structure.

Examples 24-28゜RrC synthesized from iodide according to the method of Example 23
H2CH2 ((,y,,N2.,)CH type and.

Table 10 shows fluorine-containing azides synthesized by converting alcohol into azide.

In the infrared spectra of these azides, both 280
Absorption by CH at 0-3000cm-', 2112c■
Absorption by N3 was measured at ``'1!.

In the NMR spectrum, δ=1, 1. to ppm-
CH, -proton, -C42N3 proton at 2.9ppm, and CF CH2 proton at 3.9ppm were observed.

The above analysis results support the above structure.

The same type of fluorine-containing azide as above was synthesized by the steps outlined below.

The above process was similarly applied to Rr I +CH2=CH(Cm82 m)OH diiodide.

The successful flow of the above process is shown below.

Example 29゜ 55 g of perfluoro-n-octyl iodide.

10 g of 5-hexen-1-ol and 1.6 g of azobisisobutyronitrile (AIBN) were refluxed in nitrogen at 70 to 80°C for about 5 hours to obtain a primary compound.

F (CF2). CH2CH(CH,)40H■ 5% sodium hydroxide aqueous solution 200 g to 32 g of the above compound
mQ was added and refluxed for about 24 hours.

After the reaction was completed, the above mixture was shaken with diethyl ether, the ether layer was washed with water, dried, and the solvent was distilled off to obtain the following compound.

F(CFz)scHs+cH(CHi)40H ro+1.11 The above compound was sequentially treated with methanesulfonyl chloride, potassium iodide, and sodium azide according to the method described in Example 23 to obtain the following fluorine-containing azide.

FCCF2)8C82CH(CH2)4N3.

In the infrared spectrum, C
Absorption due to H and absorption due to N3 at 2112 cm''1 were observed. In the NMR spectrum, δ=1. lppm
-CH, -proton, 2.8-3.0PPm -CH
,N, protons 3.8-4.0 ppm CF2CH2-
Protons were observed.

The above analysis results support the above structure.

Examples 30 to 33゜According to the method of Example 29, alcohols synthesized from iodide were converted into azides, and the synthesized fluorine-containing azides were shown in Table 11.
It was shown to.

In the infrared spectra of these azides, both 280
Absorption by CH at 0-3000 cm-', 2112 cm
-” absorption by N3 was observed.

In the NMR spectrum, δ=L, -CH2- at lppm
-CH2N3 protons were measured at 2.8-3.0 ppm, and CF2CH2- protons were measured at 3.8-4.0 ppm.

The above analysis results support the above structure.

Next, typical application examples of the compounds according to the present invention will be shown.

Application example 1. Antifouling treatment of polymer A coating consisting of phenol resin, epoxy resin, and polyvinyl butyral resin was applied to a glass plate and cured by heating at 200° C. for 2 hours to form a polymer coating film.

A Freon solution of the fluorine-containing azide synthesized in the example was applied to the above polymer coating film in a nitrogen atmosphere.

After exposure for 1 hour with a 600 W, low pressure mercury lamp, antifouling treatment was performed by ultrasonic cleaning in Freon for 5 minutes.

When the above polymer coating was soiled with soot from a car muffler and wiped off with a cloth, the coating without fluorine-containing azide was stained black, whereas the coating with fluorine-containing azide was less stained and wiped with a cloth. It became clean by wiping it with water.

Furthermore, in the above antifouling treatment, a similar effect was observed when the sample was heated at 130° C. for 30 minutes in a nitrogen atmosphere instead of being exposed to light.

Application example 2. The contact angle was measured for a polymer coating film formed in the same manner as in Polymer Surface Stabilization Application Example 1 and a polymer coating film antifouling treated with a fluorine-containing azide. The contact angle (by n-hexadecane) of a polymer coating film that does not use fluorine-containing azide is around 7 degrees, whereas that of a film treated with fluorine-containing azide for antifouling is around 70 degrees.
It was found that the surface was modified to have a low energy surface.

As can be seen from the above application examples, the compound of the present invention is useful as a surface stabilizer for antifouling agents.

We have also confirmed that it is useful as an intermediate.

We have also confirmed that compounds with molecular weights other than Examples, compounds with a single-branched basic skeleton, and compounds having a perfluoroalkyl chain containing an ether bond at any position can be synthesized in the same manner as described above.

〔Effect of the invention〕

It is also useful as a synthetic intermediate.

Claims (1)

[Claims] 1. A partially or fully fluorinated alkyl chain;
Alternatively, a fluorine-containing azide compound characterized by having a structure in which a polyether chain is the basic skeleton and an azide group is present via a non-fluorine functional group. 2. The fluorine-containing azide compound has the general formula (CnF_2_n_+_1)-(A)-_i(C_mH
_2_m)-(B)-_3N_3N3-(B)-_3(
C_mH_2_m)-(A)-_i(C_nF_2_n
)-(A)-1(C_mH_2_m)-(B)-_3N
＿３▲There are mathematical formulas, chemical formulas, tables, etc.▼, or, N＿３−(B)−＿３(C_mH_2_m)−(A)−
_i[CF_2O(C_tF_2_tO)_p(CF_
2O)-_qCF_2)-(A)-_i(C_mH_2
_m)-(B)_3-N_3 (However, A is -CH_2
CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or -CO_2-
B is a functional group represented by -CONHL- (L
represents an aromatic group), n is an integer from 3 to 20, m is an integer from 0 to 30, i and j are each 0 or 1 and 1
≦i+j≦2, r is an integer from 1 to 100, t is 2 or 3, and the molecule may contain t of 2 and 3 at the same time, and p and q are each 1. from 10
It is an integer up to 0. ) The fluorine-containing azide compound according to claim 1, wherein the fluorine-containing azide compound is represented by: