JP2635413B2 - Modified polypropylene oxide and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel modified polypropylene oxide which gives a resin excellent in water / oil repellency and mechanical strength by polymerization.

[Prior art] Conventionally, having a fluorinated hydrocarbon group at one end of a molecule and homopolymerizing polypropylene oxide having a polymerizable unsaturated group at the other end, or another copolymerizable monomer It is known that by copolymerization, a resin having excellent surface properties, for example, non-adhesiveness, leveling property, antistatic property, antifouling property, antifogging property, and water / oil repellency can be obtained. Examples of the above-mentioned polypropylene oxide having a fluorinated hydrocarbon group at one end of the molecule and having a polymerizable unsaturated group at the other end include, for example, JP-A-59-204144 and JP-A-61-266487. Are publicly known.
The above-mentioned JP-A-59-204144 discloses the following compound (A).

Wherein Rf is a C ₄ -C ₂₀ fluoroalkyl group; R ₁ is hydrogen or a C ₁ -C ₃ acyl group; R ₂ and R ₃ are one of hydrogen and the other is a methyl group; R ₄ is hydrogen or Methyl group; A is a divalent organic group; l, m and n are each 0 to 40, and 0 <l + m
+ N ≦ 40. JP-A-61-266487 discloses the following compound (B).

CH ₂ CRCR′COO (RO) _n Rf wherein Rf is a group containing a perfluoroalkyl group or a perfluoroalkylene glycol group, R is an alkylene residue, and R ′ is a hydrogen atom or a methyl group And n is a positive integer. The degree of polymerization of the compound (A) is at most 40. Also,
Although the polymerization degree of the compound (B) is described as a positive integer in the claims of the above publication, it is specifically 4
Only ~ 8 are disclosed.

[Problems to be solved by the invention]

The present inventors have proposed the following compounds represented by the following formulas (A) and (B) for the purpose of modifying a vinyl chloride resin: (C) and a vinyl chloride monomer were copolymerized. Although the resin thus obtained has a relatively high water repellency at a content of the monomer unit of 30 mol% based on the above compound, the mechanical strength when formed into a film cannot be measured with a tensile strength tester. There was a disadvantage that it was weak. Therefore, the compound (C) has a function of improving the surface properties of the vinyl chloride resin, but has not been put to practical use.

[Means for solving the problem]

In view of the above problems, the present inventors studied for the purpose of improving the mechanical strength of a copolymer obtained by copolymerization with a vinyl chloride monomer, and as a result, modified polypropylene oxide having a specific polymerization degree Was successfully synthesized, and it was found that the above problem could be solved by copolymerizing the modified polypropylene oxide with a vinyl chloride monomer, and the present invention was proposed.

That is, the present invention relates to the following formula [I] Is a modified polypropylene oxide represented by

JP-A-59-204144, which describes the compound (A), discloses only those having a degree of polymerization of up to 40,
The degree of polymerization is 70 like the modified propylene oxide of the present invention.
No description is given for compounds having 350350. Further, the disclosure of the above-mentioned patent publication does not suggest that the mechanical strength of the resin obtained by copolymerization with the vinyl chloride monomer is significantly improved by setting the degree of polymerization to 70 to 350. can not see.

JP-A-61-2664 in which the other compound (B) is described.
In the claims of Japanese Patent No. 87, it is described that the degree of polymerization n of the compound (B) is a positive integer, but the detailed description of the invention specifically states that the degree of polymerization of 4 to 8 Only things are shown. Further, as shown in Examples and Comparative Examples described later, the modified polypropylene oxide having a degree of polymerization of 17 has a tensile strength of 0 kg / copolymer with a vinyl chloride monomer.
Although cm ^2, and modified polypropylene oxide of polymerization degree of the present invention is from 70 to 350 indicates a 110 kg / cm ² or more tensile strength by copolymerization of vinyl chloride monomer. in this way,
The present invention provides a modified polypropylene oxide having a degree of polymerization of 70.
By setting it to 350, the tensile strength of the copolymer with the vinyl chloride monomer is remarkably improved, and a remarkably excellent effect is achieved. Even the description suggesting such excellent results of the present invention is not recognized in the above-mentioned publication.
Therefore, the above-mentioned publications merely disclose the technical idea of a low-molecular compound having a degree of polymerization of 4 to 8.

In the general formula [I], the number represented by n is from 70 to 35 in view of the mechanical strength and the surface properties of the resin obtained by forming a resin obtained by copolymerization with a vinyl chloride monomer into a film.
Must be an integer of 0. When n is less than 70, the mechanical strength of the film is significantly reduced, and when n is more than 350, the surface properties of the obtained resin are undesirably reduced. n may be an integer within the above range, but is preferably an integer of 70 to 250 in consideration of the mechanical strength, surface properties, workability, and the like of the obtained resin.

In the general formula [I], as Rf, a fluorinated hydrocarbon group in which some or all of the hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms is used without any limitation. For example, a fluorine-containing alkyl group, a fluorine-containing alkenyl group, a fluorine-containing alkynyl group,
Examples thereof include a fluorinated aryl group and a fluorinated aralkyl group. The number of carbon atoms in the fluorinated hydrocarbon group is not particularly limited, but is generally preferably selected from the range of 1 to 20, more preferably 3 to 15. Further, the ratio F / H between the fluorine atom and the hydrogen atom of the above-mentioned fluorine-containing hydrocarbon group is 1 or more, and more preferably 2 or more, so that the surface property of the copolymer with the vinyl chloride monomer becomes good. Preferred for. As the preferred fluorine-containing hydrocarbon group in the present invention, particularly, Is a group represented by

The modified polypropylene oxide of the present invention has a ratio of weight average molecular weight ( _w ) to number average molecular weight ( _n ) ( _w /
_The molecular weight distribution represented by _n ) is small, usually 1.20 or less, more preferably 1.10 or less.

The modified polypropylene oxide of the present invention generally exists as a pale yellow viscous liquid, and is soluble in common organic solvents such as chloroform, methylene chloride, tetrahydrofuran, methanol, dimethylformamide, benzene, and n-hexane. Is insoluble.

The structure of the modified polypropylene oxide of the present invention can be confirmed by an infrared absorption spectrum (hereinafter simply referred to as IR), a ¹ H-nuclear magnetic resonance spectrum (hereinafter simply referred to as ¹ H-NMR), and elemental analysis. Can be.

The degree of polymerization n of the modified polypropylene oxide is determined by gel permeation chromatography (hereinafter simply referred to as GP).
Call it C. ), The number average molecular weight _n is determined, the molecular weight of the terminal fluorinated hydrocarbon group (F _w1 ) and the polymerizable unsaturated group (F _w2 ) is subtracted from the value, and the obtained value is used as the molecular weight of the propylene oxide monomer unit. The value divided by F _w3 [n = ( _n −
F _w1 −F _w2 ) / F _w3 ]. Alternatively, it can also be determined from the integrated intensity ratio of hydrogen bonded to the polymerizable unsaturated group at the molecular end and hydrogen bonded to the fluorinated hydrocarbon group and hydrogen derived from propylene oxide determined by ¹ H-NMR. .

In the present invention, the modified polypropylene oxide may be produced by any method, but generally, the following method is suitably employed.

That is, this is a method in which propylene oxide is polymerized in the presence of a porphyrin aluminum complex and a fluorinated active hydrogen compound, and then the obtained polymer is reacted with acrylic acid halide, methacrylic acid halide or allyl halide.

As the porphyrin aluminum complex used in the present invention, those obtained by reacting an organoaluminum compound with a porphyrin compound can be used without any limitation.
The porphyrin aluminum complex preferably used in the present invention is represented by the following general formula.

In the general formula (III), the hydrocarbon group represented by R _{1 to} R ₁₂ preferably has 1 to 10 carbon atoms, such as an alkyl group, an aryl group, an alkylene group, and an alkenylene group. Is adopted. Examples of the substituent of these hydrocarbon groups include a halogen atom and an alkoxy group.

Specific examples of the porphyrin aluminum complex used in the present invention include, for example, tetraphenylporphyrin aluminum chloride, tetrabenzporphyrin aluminum chloride, tetranaphthoporphyrin aluminum chloride, tetraphenyltetrabenzporphyrin aluminum chloride, tetraphenyltetranaphthoporphyrin aluminum chloride Octaethylporphyrin aluminum chloride, tetrakispentafluorophenylporphyrin aluminum chloride, tetrakistrimethoxyphenylporphyrin aluminum chloride, tetraphenylporphyrin aluminum methoxide, tetrabenzporphyrin aluminum methoxide, tetranaphthoporphyrin aluminum methoxide, tetrafe Aluminum methoxide, tetraphenyltetranaphthoporphyrin aluminum methoxide, octaethylporphyrin aluminum methoxide, tetrakispentafluorophenylporphyrin aluminum methoxide, tetrakistrimethoxyphenylporphyrin aluminum methoxide, tetraphenylporphyrin aluminum methyl, tetramethyl Benzporphyrin aluminum methyl, tetrakispentafluorophenylporphyrin aluminum ethyl and the like.

In this case, these complexes may be linked to an organic or inorganic carrier by chemical bonding or physical adsorption.

The fluorinated active hydrogen compound used in combination with the porphyrin aluminum complex is a compound having at least one fluorine atom bonded to a carbon atom in the molecule, and a compound having one hydroxyl group or one carboxyl group without limitation. Can be used. Examples thereof include fluorinated aliphatic alcohols, fluorinated aromatic alcohols, fluorinated aliphatic carboxylic acids, and fluorinated aromatic carboxylic acids.

The fluorinated active hydrogen compound suitably used in the present invention is represented by the following general formula.

R ¹ -OH [IV] R ¹ -COOH [V] [where R ¹ is a fluorine-containing hydrocarbon group. In the above formulas [IV] and [V], the fluorine-containing hydrocarbon group represented by R ¹ is preferably a group represented by the above formula [II-a] or [II-b].

Specific examples of the fluorine-containing active hydrogen compound suitably used in the present invention are as follows.

1H, 1H-trifluoroethanol, 1H, 1H-nonafluoropentanol, 1H, 1H-nonadecafluorodecanol, 1
H, 1H-tritriacontafluoroheptadecanol, 1H,
1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 11H-eicosafluoroundecanol, 1H, 1H, 17H-dotriacontafluoroheptadecanol, 1H, 1H, 2H, 2H-nonafluorohexanol, 1H, 1H, 2H, 2H-tridecafluorooctanol, 1H, 1
H, 2H, 2H-Heptadecafluorodecanol, 1H, 1H, 2H, 2H
-Pentacosafluorotetradecanol, decafluorobenzhydrol, di (trifluoromethyl) benzyl alcohol, 1H, 1H-pentafluorobenzyl alcohol, pentafluorophenol, 2H-hexafluoroisopropanol, hexafluoro-2-methylisopropanol Phenol, perfluoro-tert-butanol, pentafluoropropionic acid, perfluoroheptanoc acid, perfluorodotecanic acid, perfluoroheptadecanoic acid, 2H-difluoroacetic acid, 6H-decafluorohexano Icacid, 10H-octadecafluorodecanoic acid, 16H-
Triacontafluorohexadecanoic acid, di (trifluoromethyl) benzoic acid, pentafluorobenzoic acid, trifluoroacetic acid, pentafluorophenoxyacetic acid, pentafluorocinamic acid, pentafluoromandelic acid, etc. It is.

The fluorinated active hydrogen compound is not limited to those specifically described above, and various fluorinated alcohols and fluorinated carboxylic acids are effectively used.

The polymerization is carried out in an atmosphere substantially free of an active gas, in a solvent or without a solvent. The solvent is not particularly limited as long as it is a non-aqueous solvent that does not react with propylene oxide or porphyrin aluminum complex. For example, methylene chloride, benzene and the like are used.

The amount of the porphyrin aluminum complex used is in the range of 0.0001 to 1 mol per 1 mol of propylene oxide.
It is particularly preferable to use it in the range of 0.0005 to 0.1 mol.
The amount of the fluorinated active hydrogen compound to be used is 1 to 50 times mol, preferably 1 mol, per mol of porphyrin aluminum complex.
It is preferably in the range of 25 to 25 moles.

The polymerization temperature is preferably in the range of 0 to 120 ° C.
Particularly, industrially, the range of 10 to 50 ° C. is preferable.

In order to introduce a polymerizable unsaturated group into the other terminal of the terminal fluorinated hydrocarbon group polypropylene oxide obtained as described above, the following method is generally employed.

That is, this is a method in which an acrylic acid halide, a methacrylic acid halide, or an allyl halide is reacted with the compound obtained by the above method without a solvent or in the presence of a solvent. This is a method utilizing the fact that the molecular terminal of the compound obtained by the above reaction has a structure of -OH group or -OAl.

As the solvent, an aprotic solvent can be used, for example, hydrocarbons such as benzene, toluene, xylene, hexane; chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; ethyl ether, tetrahydrofuran, dioxane Ethers; ketones such as acetone and methyl ethyl ketone; dimethylformamide, dimethyl sulfoxide and the like.

The molar ratio of acrylic acid halide, methacrylic acid halide or allyl halide and terminal fluorinated hydrocarbon group polypropylene oxide is 1.0 to 5.0, preferably 1.2 to 2.5.
It is.

The reaction temperature is preferably −10 ° C. to 80 ° C., preferably 0 ° C. to 50 ° C.

In this reaction, the reaction can be carried out in the presence of an alkali such as potassium hydroxide and sodium hydroxide, an alkaline salt such as potassium carbonate and sodium carbonate, and a tertiary amine such as pyridinetriethylamine.

The amount of these is usually 0.5 to 1 mol of acrylic acid halide, methacrylic acid halide or allyl halide.
To 3.0 mol, preferably 1.0 to 2.0 mol.

Thus, the modified polypropylene oxide of the present invention can be obtained.

〔effect〕

The novel modified propylene oxide according to the present invention can be homopolymerized or copolymerized with a vinyl chloride monomer or the like, and thereby has excellent surface properties such as non-adhesion, antifouling properties, antifogging properties, and water / oil repellency. Resin can be obtained.

Furthermore, utilizing the low glass transition point of this compound,
Flexibility can be imparted to the copolymer resin. In addition, since the present compound has a sufficiently large molecular weight, a resin film having excellent mechanical strength can be prepared. When the modified polypropylene oxide of the present invention is copolymerized with a vinyl chloride monomer, a copolymer having a structure in which the molecular chain of the modified polypropylene oxide is branched from the main chain composed of units based on the vinyl chloride monomer is obtained. Conceivable.
It is surprising that the mechanical strength of the obtained copolymer can be remarkably improved by setting the degree of polymerization of the molecular chain of the modified polypropylene oxide branched from the main chain to a specific value.

Further, the modified polypropylene oxide of the present invention has the following advantages because the molecular weight distribution is extremely narrow.

In the modified propylene oxide of the present invention, the polymerization activity of the polymerizable unsaturated group at one terminal of the molecule differs depending on the molecular weight. For this reason, the modified propylene oxide having a wide molecular weight distribution varies in the copolymerization with the vinyl chloride monomer, but the modified propylene oxide of the present invention has a narrow molecular weight distribution so that the copolymerization with the vinyl chloride monomer is also difficult. It proceeds uniformly and the physical properties of the obtained resin do not vary.

Further, the modified propylene oxide of the present invention has a large molecular weight and a narrow molecular weight distribution as described above, so that it contains almost no low molecular weight components. For this reason, in copolymerization with a vinyl chloride monomer, generation of a solvent-insoluble component due to a chain transfer reaction (side reaction) due to the presence of a low molecular weight component is prevented.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 《Synthesis》 Crystallized and purified tetraphenylporphyrin 1.23
g (2mmol) and 0.32ml of diethylaluminum chloride
(2.4 mmol) was reacted in 30 ml of anhydrous methylene chloride under nitrogen at room temperature for 2 hours. After the reaction, unreacted diethylaluminum chloride and methylene chloride were distilled off to obtain tetraphenylporphyrin aluminum chloride complex (purple powder). A solution obtained by adding 120 ml of purified chloroform thereto was introduced into one four-necked flask by a syringe under a nitrogen stream.

Next, 108 ml (1.6 mol) of propylene oxide and 2.18 g (10 mmol) of 1H, 1H, 5H-octafluoropentanol cooled to 0 ° C with a cooling agent were cooled to 0 ° C with a cooling agent beforehand. The reaction vessel was charged with a syringe under a nitrogen stream, and stirred with a three-one motor.
Reaction was performed at 22 ° C. for 22 hours.

After the reaction, unreacted propylene oxide and chloroform as a solvent were distilled off under reduced pressure to obtain a purple-red fluid compound.

Following the reaction vessel containing the magenta fluid compound,
1.37 g (13.2 mmol) of methacrylic acid chloride and 1.33 g (13.2 mmol) of triethylamine were added, and the reaction was carried out with stirring at room temperature under nitrogen for 65 hours.

After the reaction, 2 l of n-hexane was added, and the mixture was stirred for 1 hour under the atmosphere, then allowed to flow naturally to remove triethylamine hydrochloride and the deactivated catalyst, and then n-hexane was distilled off under reduced pressure. Then, 2 l of tetrahydrofuran and 150 g of activated carbon were added, and the mixture was stirred at room temperature for 1 hour, and tetrahydrofuran was distilled off under reduced pressure to obtain a pale yellow viscous fluid.

<< Identification >> Confirmation of chemical structure IR analysis result Peaks derived from C--O--C units at 1100 cm ^-1 1720,1170 cm ^-1 Peak from unit 1640cm ^-1 A peak derived from the unit was confirmed at 750 cm ⁻¹ , a peak derived from the —CF ₂ — unit. FIG. 1 shows the obtained chart.

¹ H-NMR analysis result (CDCl ₃ solvent) Signals assigned as follows were detected. FIG. 2 shows the obtained 270 MHz- ¹ H-NMR chart.

¹⁹ F-NMR analysis results Signals assigned as described below were detected.

Elemental analysis result The CHOF element ratio (% by weight) of the above substance is C; 64.56, H; 5.37, O; 28.53, F; 1.54, and the actual measured value (% by weight) is C; 63.80, H; 5.10, O ; 29.80, F; 1.30, and both agreed well.

GPC analysis results An A804 column manufactured by Showa Denko and a Finepack Gel 101 column manufactured by JASCO were connected, and measurement was performed at 40 ° C. using tetragudrofuran as an eluent. A calibration curve was prepared using standard polystyrene.

 The analysis results are as follows.

Number average molecular weight ( _n ) = 10400 The molecular weights of the methacryloyl group and the H (CF ₂ ) ₄ CH ₂ O group are F _w1 = 69 and F _w2 = 231, respectively, so that the degree of polymerization n of the modified propylene oxide is It is.

《Conclusion》 From the above analysis results, the compound obtained in this experiment And concluded.

Example 2 << Synthesis >> Chloroform 1 was added to tetraphenylporphyrin aluminum complex (2.5 mmol) prepared in the same manner as in Example 1.
After adding 00 ml, the mixture was introduced into a 300 ml four-necked flask and cooled to 0 ° C. Next, 5.45 g (25 mmol) of 1H, 1H, 5H-octafluoropentanol and 100 ml (1480 mmol) of propylene oxide cooled to 0 ° C. were added by a syringe under nitrogen, and polymerization was carried out for 56 hours while stirring with a three-one motor. After the reaction, unreacted propylene oxide and chloroform as a solvent were distilled off under reduced pressure to obtain a red-purple fluid.

Following this reaction mixture, methacrylic acid chloride
3.13 g (30.25 mmol) and triethylamine 3.03 g (30.25 mm
ol), and the reaction was carried out with stirring at room temperature under nitrogen for 62 hours. Thereafter, purification was performed in the same manner as in Example 1 to obtain a pale yellow viscous fluid.

<< Identification >> Confirmation of Chemical Structure Results of IR, ¹ H-NMR, and ¹⁹ F-NMR Analyzes All the analyzes showed the same absorption spectrum as that described in Example 1. However, the intensity ratio of the peak derived from the methacryloyl group and the peak derived from the fluoroalkyl group to the other peaks increased (third.
Figure).

 Elemental analysis results The elemental ratio of C, H, O, and F (% by weight) of the above substance was C; 60.28, H; 9.80, O; 26.43, F; 3.49, and the actually measured value (% by weight) was C; , H; 9.70, O; 27.50, F; 3.30, and both agreed well.

GPC analysis result Number average molecular weight _n = 4360 Propylene oxide polymerization degree n is It is.

《Conclusion》 The compound obtained in this experiment And concluded.

Example 3 << Synthesis >> In Example 1, the charged amount of propylene oxide was
A pale yellow viscous fluid was obtained in the same manner except that the polymerization time was changed to 162 ml (2.4 mol) and the polymerization time was set to 45 hours.

<< Identification >> Confirmation of Chemical Structure Results of IR, ¹ H-NMR, and ¹⁹ F-NMR Analyzes All the analyzes showed the same absorption spectrum as that described in Example 1. However, the intensity ratio of the peak derived from the methacryloyl group and the peak derived from the fluoroalkyl group to the other peaks decreased (fourth).
Figure).

 Elemental analysis results The elemental ratio of C, H, O, and F (% by weight) of the above substance is C; 61.57, H; 10.19, O; 27.13, F; 1.11. The measured value (% by weight) is C; , H; 10.03, O; 28.10, F; 0.94, and both agreed well.

GPC analysis result Number average molecular weight _n = 13640 Propylene oxide polymerization degree n is It is.

《Conclusion》 The compound obtained in this experiment And concluded.

Example 4 << Synthesis >> To a tetraphenylporphyrin aluminum chloride complex (2 mmol) prepared in the same manner as in Example 1, 120 ml of chloroform, 4.32 g (10 mmol) of 1H, 1H, 9H-hexadecafluorononanol were added, and 14 The mixture was transferred to a flask with a syringe under nitrogen and cooled to 0 ° C.

162 ml (2.4 mol) of propylene oxide, which had been cooled (0 ° C.) in advance, was added to this container with a syringe under a stream of nitrogen, and polymerized for 19 hours. After the reaction, unreacted propylene oxide and chloroform as a solvent were distilled off to obtain a red-purple viscous compound.

This was reacted with an acid chloride and an amine in the same manner as in Example 1 and purified with activated carbon to obtain a pale yellow viscous fluid.

"Identification" in the confirmation of the chemical structure IR analysis 1100 cm ^-1 to a peak 1720,1170Cm ^-1 derived from the C-O-C units Peak from unit 1640cm ^-1 At 750 cm ⁻¹ , a peak derived from the unit, a peak derived from the —CF ₂ − unit was confirmed. FIG. 5 shows the obtained chart.

¹ H-NMR analysis result (CDCl ₃ solution) Signals assigned as follows were detected.

¹⁹ F-NMR analysis results Signals assigned as described below were detected.

GPC analysis results The analysis results are as follows. _n = 14000 _w / _n = 1.12 The degree of polymerization n of propylene oxide is It is.

《Conclusion》 The compound obtained in this experiment is And concluded.

Examples 5 to 10 Except for changing the kind of the fluorine-containing active hydrogen compound, the charged molar ratio of propylene oxide and the porphyrin aluminum complex, and the kind of the active halogen compound, all are shown in Table 1 by the method shown in Example 1. Compound was obtained.

The compounds were identified using ¹ H-NMR, ¹⁹ F-NMR, IR and GPC.

Application Examples The suspension polymerization of the modified polypropylene oxide obtained in Examples 1 to 9 and a vinyl chloride monomer was performed at 50 ° C. for 5 hours. The content of the unit based on the modified polypropylene oxide in the obtained copolymer and the insoluble content in tetrahydrofuran at 66 ° C. were measured, and the results are shown in Table 2.

Next, the roll processability of the obtained copolymer, the contact angle of water,
The transparency and tensile strength were measured, and the results are shown in Table 2.

However, the roll processability was measured by using a small heat roll machine (5RK4ORGN-A type, manufactured by Oriental Motor Co., Ltd.) using a mixture of 100 parts by weight of the copolymer and 4 parts by weight of the tin-based heat stabilizer. Roll processing was performed at 130 ° C., and the results were indicated by the following criteria according to the maximum temperature at which roll processing was possible.

Good: 130 ° C. or more Slightly good: 100 to 130 ° C. Bad: 100 ° C. or less Transparency was measured by measuring the transmittance of light at 500 nm and indicated by the following criteria.

Good: 85% or more Slightly good: 70-85% Slightly poor: 55-70% Bad: 55% or less The contact angle of water was measured at 25 ° C and 50% humidity, one minute after contact with water droplets. .

Furthermore, the following modified polypropylene oxide having a low degree of polymerization Table 2 shows the results when Comparative Example 1 and Comparative Example 2 were performed in the same manner as in Application Examples 1 to 9 except that the modified polypropylene oxide was used, and Comparative Example 3 was performed when no modified polypropylene oxide was used.
Are also shown.

[Brief description of the drawings]

FIG. 1 is a chart of an infrared absorption spectrum of the compound obtained in Example 1. FIG. 2 is a ¹ H-nuclear magnetic resonance spectrum chart of the compound obtained in Example 1. FIGS. 3, 4 and 5 are charts of infrared absorption spectra of the compounds obtained in Example 2, Example 3 and Example 4, respectively.

Claims (2)

(57) [Claims] (1) General formula A modified polypropylene oxide represented by the formula: 2. A method of polymerizing propylene oxide in the presence of a porphyrin aluminum complex and a fluorine-containing active hydrogen compound, and then reacting the obtained polymer with acrylic acid halide, methacrylic acid halide or allyl halide. A method for producing a modified polypropylene oxide according to claim (1).