JP6326966B2 - Method for producing fluorine-containing urethane (meth) acrylate - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing urethane (meth) acrylate. More specifically, the present invention relates to a method for producing a fluorinated urethane (meth) acrylate in which a fluorinated alcohol and an isocyanatoalkyl (meth) acrylate are reacted.

  Fluorine-containing urethane (meth) acrylate is effectively used as a fluorine-based surfactant. This compound can be obtained by reacting a fluorinated alcohol and an isocyanatoalkyl (meth) acrylate (Patent Documents 1 and 2). In this reaction, an organometallic catalyst such as dibutyltin dilaurate or a tertiary amine such as triethylamine, benzyldimeramine, triethylenediamine or methylmorpholine is used as the urethanization accelerating catalyst. For example, the reaction time is long at 45 ° C for a whole day and night at 70 ° C for 4 hours or 85 ° C for 6 hours.

  Further, the present applicant has obtained a fluorinated polyether (meth) acrylate from a fluorinated polyether diol and an isocyanatoalkyl (meth) acrylate (Patent Document 3), in which case dibutyltin dilaurate is used as a reaction catalyst. Used and allowed to react at 40 ° C. for 3 hours. In addition, Patent Document 3 also mentions that an amine-based catalyst such as 1,8-diazabicyclo [5.4.0] undec-7-ene can be used, but there is no example related thereto.

JP-A-62-205054 JP 2008-115258 A JP 2008-38015 A Japanese Patent No. 4673604 WO 2007/080949 A1

  The object of the present invention is to use an amine-based catalyst with less environmental impact when reacting a fluorinated alcohol and an isocyanatoalkyl (meth) acrylate, and to produce a fluorinated urethane (meth) acrylate in a high yield in a short reaction time. It is to provide a method of manufacturing.

The object of the present invention is to provide a general formula
R _f -A-OH (I)
(Wherein R _f is a linear or branched perfluoroalkyl group that may contain O, S, or N atoms, or a polyfluoroalkyl in which part of the fluorine atoms of the perfluoroalkyl group is substituted with a hydrogen atom. A fluorine-containing alcohol represented by the formula (A is an alkylene group having 1 to 6 carbon atoms) and an isocyanatoalkyl (meth) acrylate compound at a ratio of 0.3 to 1.11 mol% with respect to the fluorine-containing alcohol. In the presence of a nitrogen-containing heterocyclic compound catalyst such as 1,8-diazabicyclo [5.4.0] undec-7-ene or N, N-dimethyl-4-aminopyridine at room temperature to 60 ° C. This is achieved by a method for producing a fluorine-containing urethane (meth) acrylate characterized by reacting for 0.5 to 1.0 hour.

  The reaction using a tertiary amine or an organic tin compound as a catalyst, which has been used in the past, requires a reaction time of several hours, and the conversion rate when using an organic tin compound is only about 90% and reaches its peak. In contrast, the organic tin compound used is a high environmental impact compound, whereas the nitrogen-containing heterocyclic compound catalyst used in the present invention has not only a lower environmental impact, but also a reaction time of 0.5% and 95%. It shows an excellent conversion rate of 100% in about 1 hour, making it possible to produce the desired fluorine-containing urethane (meth) acrylate.

General formula
R _f -A-OH (Ia)
R _f : linear or branched perfluoroalkyl that may contain O, S or N atoms
Or a part of the fluorine atom of the perfluoroalkyl group is a hydrogen atom.
Substituted polyfluoroalkyl groups
A: As a fluorine-containing alcohol represented by a C1-C6 alkylene group, the following are mentioned, for example.
C _p F _{2p + 1} (CH ₂ ) _q OH (Ia)
C _p F _2p H (CH ₂ ) _q OH (Ia ′)
p is 1-10, preferably 4-8
q is 1 to 6, preferably 2
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b (CH ₂ CH ₂ ) _c OH (IIa)
n: 1-6, preferably 2-4
a: 1 to 4, preferably 1
b: 0-3, preferably 1-2
c: 1 to 3, preferably 1
C _m F _{2m + 1} O (CF (CF ₃ ) CF ₂ O] _d CF (CF ₃ ) (CH ₂ ) _e OH (IIIa)
m: 1-3, preferably 3
d: 0 to 100, preferably 1 to 10
e: 1 to 3, preferably 1

Examples of the fluorinated alcohol represented by the general formula [Ia] include 2,2,2-trifluoroethanol (CF ₃ CH ₂ 0H), 3,3,3-trifluoropropanol (CF ₃ CH ₂ CH ₂ OH). ), 2,2,3,3,3-pentafluoropropanol (CF ₃ CF ₂ CH ₂ 0H), 3,3,4,4,4-pentafluorobutanol (CF ₃ CF ₂ CH ₂ CH ₂ OH), 2,2,3,3,4,4,5,5,5-nonafluoropentanol (CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ 0H), 3,3,4,4,5,5,6, 6,6-nonafluorohexanol (CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ OH), 3,3,4,4,5,5,6,6,7,7,8,8,8-tri Examples include decafluorooctanol (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ OH).

Examples of the fluorine-containing alcohol represented by the general formula [Ia ′] include 2,2,3,3-tetrafluoropropanol (HCF ₂ CF ₂ CH ₂ OH), 2,2,3,4,4,4- Hexafluorobutanol (CF ₃ CHFCF ₂ CH ₂ OH), 2,2,3,3,4,4,5,5-octafluoropentanol (HCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OH) . Examples of q = 0 include 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropanol (CF ₃ ) ₂ CHOH and the like.

  The fluorine-containing alcohol represented by the general formula [IIa] is described in Patent Document 4, for example.

In the hexafluoropropene oxide oligomer alcohol represented by the general formula [IIIa], a compound having m = 1 and e = 1 is described in Patent Document 5 and synthesized through the following steps.
Fluorine-containing ether carboxylic acid alkyl ester represented by the general formula CF ₃ O [CF (CF ₃ ) CF ₂ O] _n CF (CF ₃ ) COOR (R: alkyl group, n: integer of 0 to 12), hydrogen Reduction reaction is performed using a reducing agent such as sodium borohydride.

Isocyanatoalkyl (meth) acrylate compounds that react with these fluorine-containing alcohol compounds include isocyanatomethyl (meth) acrylate, isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, isocyanatobutyl (meth) Acrylate is used, but in terms of supply, it is a commercial product Karenz AOI (CH ₂ = CHCOOCH ₂ CH ₂ NCO) or Karenz MOI (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ NCO) is preferred.

The reaction between the fluorinated alcohol compound and the isocyanatoalkyl (meth) acrylate compound is carried out in the presence of a nitrogen-containing heterocyclic compound catalyst. As the nitrogen-containing heterocyclic compound , 1,8-diazabicyclo [5.4.0] undec-7-ene or N, N-dimethyl-4-aminopyridine is used.

The isocyanatoalkyl (meth) acrylate compound is used in an equimolar amount or a small excess amount with respect to the fluorine-containing alcohol compound. The nitrogen-containing heterocyclic compound catalyst is preferably used in a proportion of about 0.3 to 1.11 mol% with respect to the fluorinated alcohol compound, and side reactions occur even when a proportion higher than this, for example, about 3.5 mol% is used. The conversion is slightly reduced. On the other hand, if the amount of catalyst is too large, the heat generation is intense and the reaction cannot be controlled. Conversely, if the amount of catalyst is too small, the conversion rate does not exceed 90% in the desired reaction time. On the other hand, when a triethylamine catalyst is used at a ratio of about 0.3 to 2.0 mol%, it takes several hours to obtain a conversion rate of nearly 100%, whereas a nitrogen-containing heterocyclic compound is required. When a catalyst is used, the desired conversion can be obtained in 0.5 hour or 1.0 hour.

  The reaction can be carried out in the presence or absence of a solvent, but in view of economy and environment, the reaction in the absence of a solvent is preferable. However, when the fluorinated alcohol is solid, it is preferable to use an ether solvent such as glyme having a higher polarity than a hydrocarbon solvent such as low-polarity toluene. The reaction temperature is not particularly limited, but is preferably about room temperature to about 60 ° C. for ease of control and suppression of undesired polymerization in the reaction system. The reaction is carried out at 50 ° C.

  Next, the present invention will be described with reference to examples.

Example 1
To a 100 ml three-necked flask equipped with a thermocouple, Dimroth and septum, under a nitrogen gas atmosphere, CF ₃ (CF ₂ ) ₅ OH [FA-6] 6.0 ml (10.0 g; 27.5 mmol) and 1,8-diazabicyclo [5.4.0] Undec-7-ene [DBU] 0.02 ml (0.02 g; 0.134 mmol; 0.488 mol% with respect to FA-6) was added and heated to 50 ° C., where 2-isocyanatoethyl acrylate ( Showa Denko product Karenz AOI) 3.6 ml (4.07 g; 28.8 mmol) was added dropwise to initiate the reaction.

^When the disappearance of FA-6 was confirmed by ¹ H NMR, the reaction was terminated by cooling. The reaction tracking was performed by calculating from the peak of olefin on the high magnetic field side of acrylate or methacrylate.

Reaction time (hours) conversion (%)
0.2 95
0.3 96

Example 2
In Example 1, 0.017 g (0.139 mmol; 0.507 mol% based on FA-6) of N, N-dimethyl-4-aminopyridine [DMAP] was used instead of DBU.
Reaction time (hours) conversion (%)
0.2 89
0.5 95
1.0 100

Comparative Example 1
In Example 1, 0.016 g (0.158 mmol; 0.575 mol% based on FA-6) of triethylamine [TEA] was used instead of DBU.
Reaction time (hours) conversion (%)
0.1 49
1.0 73
6.0 99

Comparative Example 2
In Comparative Example 1, 0.036 g (0.356 mmol; 1.30 mol% based on FA-6) of TEA was used.
Reaction time (hours) conversion (%)
0.5 64
1.0 73
6.0 99

Comparative Example 3
In Example 1, DBU was not used.
Reaction time (hours) conversion (%)
3.0 11
21.5 61
24.0 64
30.0 74
45.5 85
53.0 86
69.5 90

Example 3
In Example 1, the reaction was carried out by varying the amount of DBU.
g mmol mole% Reaction time (hr) Conversion (%)
0.020 0.134 0.488 0.2 95
0.020 0.134 0.488 0.3 96
0.041 0.268 0.976 0.5 100
0.143 0.938 3.415 0.5 95

Examples 4-8
In Example 3, various fluorine-containing alcohols were used in place of FA-6, and the reaction was performed for 0.5 hour at a DBU usage ratio of about 1 mol%. Since FA-8 and DTFA103 were solid, 30 ml of glyme (1,2-dimethyloxyethane) was used as a solvent. The obtained results are shown in the following table together with the results of Example 3.
FA-4: CF ₃ (CF ₂ ) ₃ OH
FA-8: CF ₃ (CF ₂ ) ₇ OH
DTFA103: CF ₃ (CF ₂ ) ₃ CH ₂ (CF ₂ ) ₅ CH ₂ CH ₂ OH
C ₄ F ₉ (CH ₂ CF ₂ ) (CF ₂ CF ₂ ) ₂ (CH ₂ CH ₂ ) OH
_{PO3OH: CF 3 (CF 2)} 2 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH
HFIPA: (CF ₃ ) ₂ CH (OH)
Fluorine-containing alcohol Karenz AOI DBU conversion rate
Example type mmol ( mole ) (mol%) (%)
4 FA-4 32.5 32.0 1.03 100
3 FA-6 27.5 28.8 0.98 100
5 FA-8 30.2 32.0 1.00 100
6 DTFA103 18.9 20.0 0.88 100
7 PO3OH 20.7 21.6 0.97 100
8 HFIPA 59.5 60.9 1.01 100

Examples 9-14
In Examples 4, 3, and 5-8, 2-isocyanatoethyl methacrylate (Showa Denko Karenz MOI) was used in place of 2-isocyanatoethyl acrylate as the isocyanatoalkyl (meth) acrylate. The results obtained are shown in the following table.
Fluorine-containing alcohol Karenz MOI DBU conversion rate
Example type mmol ( mole ) (mol%) (%)
9 FA-4 32.5 31.8 1.03 92
10 FA-6 27.5 28.3 0.98 91
11 FA-8 15.1 15.5 1.11 100
12 DTFA103 18.9 19.8 0.88 100
13 PO3OH 20.7 21.2 0.97 100
14 HFIPA 59.5 59.3 1.01 100

Claims (4)

General formula
R _f -A-OH (I)
(Wherein R _f is a linear or branched perfluoroalkyl group that may contain O, S, or N atoms, or a polyfluoroalkyl in which part of the fluorine atoms of the perfluoroalkyl group is substituted with a hydrogen atom. A fluorine-containing alcohol represented by the formula (A is an alkylene group having 1 to 6 carbon atoms) and an isocyanatoalkyl (meth) acrylate compound at a ratio of 0.3 to 1.11 mol% with respect to the fluorine-containing alcohol. In the presence of a nitrogen-containing heterocyclic compound catalyst such as 1,8-diazabicyclo [5.4.0] undec-7-ene or N, N-dimethyl-4-aminopyridine at room temperature to 60 ° C. A process for producing a fluorine-containing urethane (meth) acrylate, characterized by reacting for 0.5 to 1.0 hour. The fluorine-containing alcohol represented by the general formula [I] is represented by the general formula
C _p F _{2p + 1} (CH ₂ ) _q OH (Ia)
Or
C _p F _2p H (CH ₂ ) _q OH (Ia ′)
The method for producing a fluorinated urethane (meth) acrylate according to claim 1, wherein the compound is represented by the formula (wherein p is 1 to 10 and q is 1 to 6). The fluorine-containing alcohol represented by the general formula [I] is represented by the general formula
C _n F _{2n + 1} (CH ₂ CF ₂ ) _a (CF ₂ CF ₂ ) _b (CH ₂ CH ₂ ) _c OH (IIa)
(Wherein n is 1 to 6, a is 1 to 4, b is 0 to 3, and c is 1 to 3). Production of fluorinated urethane (meth) acrylate according to claim 1 Law. The fluorine-containing alcohol represented by the general formula [I] is represented by the general formula
C _m F _{2m + 1} O (CF (CF ₃ ) CF ₂ O] _d CF (CF ₃ ) (CH ₂ ) _e OH (IIIa)
The method for producing a fluorinated urethane (meth) acrylate according to claim 1, wherein the compound is represented by the formula (wherein m is 1 to 3, d is 0 to 100, and e is 1 to 3).