JPH07149889A - Production of fluorine-containing alkyl polyether polymer - Google Patents

Abstract

PURPOSE:To obtain the polymer having high molecular weight and narrow molecular weight distribution and useful as a production raw material for lubricating oil, surfactant, etc., by copolymerizing a perfluoroalkylene oxide with an alkylene oxide in the presence of a porphyrin metal complex. CONSTITUTION:Tetraphenylporphyrin and diethylaluminum chloride, etc., are charged to a pressure-resistant glass autoclave and reacted with each other in methylene chloride for 3hr. The reaction product is vacuum-dried at 50 deg.C for 3hr to remove unreacted materials and obtain a porphyrin metal complex of formula [R1 to R12 are H or a (substituted)hydrocarbon group; X is H, a halogen, an alkyl, an alkoxy, phenoxy, an alkylthio or hydroxy], etc. The fluorine-containing polymer is produced by introducing a perfluoroalkylene oxide (e.g. hexafluoropropylene oxide) and an alkylene oxide (e.g. propylene oxide) into a reaction vessel cooled with dry ice-methanol and copolymerizing the components in the presence of the above complex as a catalyst under ice- cooling for 16hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing alkyl polyether polymer. More specifically, it relates to a method for producing a fluorine-containing alkyl polyether polymer using a porphyrin metal complex as a catalyst.

[0002]

2. Description of the Related Art Fluorine-containing alkyl polyether polymers are chemically stable polyethers having perfluoroalkyl groups, and are used as intermediates in the production of lubricating oils and surfactants, or in the production of special rubbers. Is useful as As the initiator for obtaining the polymer of perfluoroalkylene oxide, monovalent metal fluorides such as cesium fluoride and potassium fluoride are known, but the obtained polymer has a low molecular weight and also has a molecular weight distribution. Since it is wide, purification and other costs are high in practical use, which makes it expensive.

On the other hand, the porphyrin metal complex used to obtain a polymer of alkylene oxide has no effect as a polymerization catalyst of perfluoroalkylene oxide alone.

[0004]

SUMMARY OF THE INVENTION It is desired that the fluorine-containing alkyl polyether polymer used for lubricating oil or the like be chemically stable. In addition, in addition to that, if a substance having a low molecular weight is contained, it becomes a low boiling point and thus there is a problem that purification is required, so that the molecular weight is high,
A narrow molecular weight distribution was desired.

[0005]

Means for Solving the Problems The present inventors have studied various catalysts in order to solve the above technical problems, and as a result, by copolymerizing perfluoroalkylene oxide and alkylene oxide with a porphyrin metal complex as a catalyst, The inventors have found that a fluorine-containing alkyl polyether polymer having a high molecular weight and a narrow molecular weight distribution can be obtained, and completed the present invention.

That is, the present invention is a method for producing a fluorine-containing alkyl polyether polymer, which comprises copolymerizing perfluoroalkylene oxide and alkylene oxide in the presence of a porphyrin metal complex.

The porphyrin metal complex in the present invention is
Known compounds can be used without any limitation. Porphyrin metal complexes that can be preferably used in the present invention are porphyrin aluminum complexes and porphyrin zinc complexes, which can be represented by the following formulas [I] and [II].

[0008]

[Chemical 1]

[0009]

[Chemical 2]

(In the formula, R _{1 to} R ₁₂ are hydrogen atoms or substituted or unsubstituted hydrocarbon groups, and R ₃ and R ₄ , R ₆ and R ₇ ,
R ₉ and R _10, and R ₁₂ and R ₁ may each form a condensed ring, R is a hydrocarbon group, and X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenoxy group, an alkylthio group. Or it is a hydroxyl group. ) The above general formulas R _{1 to} R ₁₂
And the hydrocarbon group represented by R has a carbon number of 1 to
It is preferably in the range of 10, and an alkyl group, an aryl group, an alkylene group, an alkenylene group or the like is adopted.
Among these, examples of the substituent of the substituted hydrocarbon group include a halogen atom and an alkoxy group.

The metals in the porphyrin metal complex used in the present invention include magnesium, vanadium, chromium, manganese, in addition to the above-mentioned aluminum and zinc.
Iron, cobalt, nickel, copper, ruthenium, rhodium,
Metals such as palladium and cadmium can be mentioned.

Specific examples of the porphyrin metal complex preferably used in the present invention include tetraphenylporphyrin aluminum chloride, tetrabenzporphyrin aluminum chloride, tetraphenylporphyrin aluminum methoxide, tetraphenylporphyrin aluminum methyl, tetrabenzporphyrin aluminum methyl. , Porphyrin aluminum complexes such as tetraphenylporphyrin aluminum ethyl and tetrakispentafluorophenylporphyrin aluminum ethyl; examples of the polyphyrin zinc complex include porphyrin zinc complexes such as tetraphenylporphyrin zinc ethyl and N-methyltetraphenylporphyrin zinc thiolate.

The amount of the porphyrin metal complex used may be a catalytic amount in a general polymerization reaction, but 0.1 to 10 parts by weight, particularly 0.5 to 100 parts by weight of the total amount of perfluoroalkylene oxide and alkylene oxide is used. -5 parts by weight is preferred.

The perfluoroalkylene oxide in the present invention is not particularly limited as long as it is known, and it can be used alone or in combination of two or more kinds. Specific examples thereof include hexafluoropropylene oxide and tetrafluoroethylene oxide.

The alkylene oxide in the present invention is not particularly limited as long as it is a known one, and it can be used alone or in combination of two or more kinds. Specifically, an aliphatic alkylene oxide having an epoxy group such as ethylene oxide, propylene oxide, 1-butylene oxide, epichlorohydrin, and trifluoropropylene oxide; an alicyclic alkylene oxide having an epoxy group such as cyclopentene oxide and cyclohexene oxide. An aromatic alkylene oxide having an epoxy group such as styrene oxide and the like can be mentioned; among them, an aliphatic alkylene oxide is preferable, and ethylene oxide and propylene oxide are particularly preferable.

The copolymerization ratio of perfluoroalkylene oxide and alkylene oxide is not particularly limited, but in order to suppress the progress of the polymerization reaction and the formation of the obtained alkylene oxide homopolymer, perfluoroalkylene oxide is used. The alkylene oxide is 10 to 100 parts by weight, preferably 30 to 1 with respect to 100 parts by weight.
It is preferably in the range of 00 parts by weight.

The polymerization may be carried out in the absence of a solvent or in the presence of an organic solvent such as an aromatic hydrocarbon such as benzene, toluene, xylene or a halogenated hydrocarbon such as dichloromethane. The polymerization temperature is −30 to 200 ° C., especially −20 to 100 ° C.
C is preferred. Polymerization is carried out in an inert gas such as nitrogen. After the reaction is completed, the reaction is stopped with an acid such as acetic acid or hydrochloric acid, washed with methanol, water or the like, and dried under reduced pressure to obtain a dry polymer.

[0018]

EFFECTS OF THE INVENTION By using the production method of the present invention, it is possible to obtain a fluorine-containing alkyl polyether polymer which is required for a lubricating oil and the like and which is chemically stable and has a high molecular weight and a narrow molecular weight distribution. As a result, it was possible to omit the separation and purification step because impurities such as low-boiling substances were scarcely present during production.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Tetraphenylporphyrin 0.12 g (0.2 mmol) and diethylaluminum chloride 0.024 g (0.2 m) were placed in a pressure-resistant glass autoclave having a capacity of 100 ml.
mol) and 5 ml of methylene chloride were added and the mixture was reacted for 3 hours with stirring, and then vacuum dried at 50 ° C. for 3 hours to remove unreacted diethylaluminum chloride. Next, while the container was cooled with dry ice-methanol, 17 g of hexafluoropropylene oxide and 6 g of propylene oxide were introduced, the mixture was stirred for 1 hour, the temperature was raised to 0 ° C., and the mixture was reacted for 16 hours under ice cooling. After the reaction, the container was returned to room temperature and the unreacted raw materials were distilled off by an evaporator to obtain 15 g of a viscous liquid polymer.

Subsequently, the porphyrin aluminum complex was separated by filtration, and in the IR of the obtained polymer, absorption based on C—H stretching vibration derived from the methyl group of propylene oxide was 3000 cm ⁻¹ , and trifluoromethyl hexafluoropropylene oxide. Absorption based on C—F stretching vibration derived from the group is 1400 to 1000 cm ⁻¹ , and absorption based on C═O stretching vibration derived from acid fluoride of the polymerization end group is 1780.
cm ⁻¹ was observed, and the absorption derived from the raw material epoxy group had disappeared.

As a result of elemental analysis, C: 31.9%, H:
2.6%, F; 51.4%, and hexafluoropropylene oxide and propylene oxide were introduced into the polymer at an approximate ratio of 1: 1. The molecular weight of the polymer was determined by GPC to have a number average molecular weight of 6000 and a molecular weight distribution (Mw /
Mn) was 1.28.

Examples 2 to 4 In the same manner as in Example 1 except that the porphyrin compounds shown in Table 1 were used in place of tetraphenylporphyrin and the organometallic compounds shown in Table 1 were used in place of diethylaluminum chloride. The reaction was carried out. As a result, an IR spectrum similar to that of Example 1 was observed in each case,
The absorption derived from the raw material epoxy group has disappeared. The elemental analysis results were almost the same as in Example 1. The molecular weight and molecular weight distribution of the polymer are shown in Table 1.

[0024]

[Table 1]

Comparative Example 1 17 g of hexafluoropropylene oxide and 6 g of propylene oxide were introduced in a state where a pressure-resistant glass autoclave having a capacity of 100 ml was cooled with dry ice-methanol, and after stirring for 1 hour, the temperature was raised to 0 ° C. and ice-cooled. Bottom 1
After reacting for 6 hours, the container was returned to room temperature and unreacted substances were separated to obtain 5 g of a transparent liquid. The polymer obtained is described in Example 1.
The same IR spectrum and elemental analysis results were shown as
The number average molecular weight was as low as 800 in the molecular weight measurement by PC.

Comparative Example 2 Tetraphenylporphyrin and diethylaluminum chloride were reacted in the same manner as in Example 1 using a pressure-resistant glass autoclave having a capacity of 100 ml and vacuum dried. Then, while the container was cooled with dry ice-methanol, only 17 g of hexapropylene oxide was introduced, and Example 1 was used.
When reacted in the same manner as above, the reaction did not proceed at all.

Examples 5 to 6 Polymerization was carried out in the same manner as in Example 1 except that only the amount of hexafluoropropylene oxide was changed to 34 g and 50 g, and the yields were 16.
It was 2g and 15.5g. The IR and elemental analysis results of the obtained polymer were almost the same as in Example 1, and the molecular weights of all the polymers were number average molecular weight 6200 and molecular weight distribution (Mw
/ Mn) was 1.33. The ratio of hexafluoropropylene oxide to propylene oxide-based repeating units was about 1: 1.

Claims (1)

[Claims] 1. A method for producing a fluorine-containing alkyl polyether polymer, which comprises copolymerizing perfluoroalkylene oxide and alkylene oxide in the presence of a porphyrin metal complex.