JPS6114196B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention involves copolymerizing derivatives of acrylic acid, methacrylic acid, vinylpyridine, etc. containing perfluoroalkenyl phenyl ether as a component of a quaternary ammonium salt, singly or with each other, or with other addition-polymerizable monomers. The present invention relates to a water and oil repellent containing a polymer obtained by the method as an active ingredient. The present inventors have developed a technology for producing perfluoroalkenyl phenyl ether by reacting a dimer or trimer obtained by oligomerization of hexafluoropropene with an aromatic compound having a hydroxyl group ( While researching compounds derived from the perfluoroalkenyl phenyl ether (Japanese Patent Application No. 49-26959; Japanese Patent Publication No. 57-56454), it was discovered that a fluorine-containing surfactant containing the above group as a constituent has oil repellency. Taking note of this, we attempted to obtain a polymeric water and oil repellent by incorporating this into a polymer component. However, contrary to expectations, very little oil repellency can be obtained by using polymers incorporating these highly branched perfluoroalkenyl phenyl ethers alone, and the objective can only be achieved by using quaternary ammonium salts. I was able to do that. The present invention is based on this fact and consists of the following configuration. Quaternary ammonium salt with perfluoroalkenyl phenyl ether group: [In the formula, R ₁ is hydrogen or a methyl group, R is a perfluorohexenyl group or perfluorononenyl group, X is a monovalent anion, and n represents an integer of 2 or 3] alone. Alternatively, it is a water and oil repellent agent containing as an active ingredient a polymer obtained by addition polymerization with each other or coaddition polymerization with other addition polymerizable monomers. In this case, X is not particularly limited, and may be a low-molecular anion such as chlorine or bromine that generally forms a quaternary ammonium salt, or a carboxylic acid or sulfonic acid having a perfluoroalkyl group. The phenyl group of perfluoroalkenyl phenyl ether is preferably a phenyl group without a substituent, but may have a low molecular substituent such as a halogen, nitro group, hydroxyl group, methyl group, or cyano group, Substituents with such a low molecular weight have little effect on water and oil repellency. Perfluoroalkenyl phenyl ether is
This is introduced into the monomer by reacting a perfluoroalkenyloxyphenyl alkylene halide obtained by haloalkylation with a haloalkyl ether such as halomethyl ether or haloethyl ether with a tertiary nitrogen atom. This reaction is carried out in a solvent such as acetonitrile in the presence of a polymerization inhibitor such as hydroquinone. The resulting quaternary ammonium salt can be substituted with a suitable anion, if desired. The quaternary ammonium salt-containing monomer thus obtained is subjected to a well-known method, that is, solution polymerization, emulsion polymerization, bulk polymerization, or suspension polymerization in the presence of a radical initiator or under irradiation with ultraviolet rays, radiation, etc. can also be polymerized. Solution polymerization using an organic radical initiator is generally preferred. At this time, the double bond in the perfluoroalkenyl group does not participate in polymerization due to steric hindrance. In addition, these monomers are copolymerized with other fluorine-containing monomers having polymerizable double bonds, such as acrylic acid or methacrylic acid esters having perfluoroalkyl groups, or non-fluorine monomers, to form water and oil repellent polymers. It is also possible to obtain When using the water and oil repellent of the present invention on fibers, appropriate flexibility and texture may be required, and in this case, by copolymerizing non-fluorine monomers,
A water and oil repellent that meets such requirements can be obtained. The use of non-fluorine-based monomers, such as acrylic esters, may cause a decrease in water and oil repellency, but should be used within the range that does not cause any practical problems in accordance with the water and oil repellency required for textiles. do it. When a known polymer made of acrylic acid or methacrylic acid ester having a perfluoroalkyl group is mixed with the obtained polymer, the oil repellency can be further improved. In addition, the polymer of the present invention has antistatic properties as well as water and oil repellency, and has the advantage that the amount of antistatic agents that generally have a negative effect on water and oil repellency can be reduced. . A reference example (manufacturing method) and an example (performance test) will be described below. Reference example 1 N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,
N-dimethylammonium chloride Production of: 2-dimethylaminoethyl methacrylate 7.86
g (0.05 mol) and p-perfluorononenyloxybenzyl chloride 28.63 g (0.05 mol)
and 0.5g of hydroquinone in 200ml of acetonitrile
ml and reacted at 50±5°C for 8 hours with stirring. Most of the reactants precipitate, but when 100 ml of benzene is added to the reaction layer, all the small amount of reactants dissolved in the acetonitrile also precipitates. The precipitate was separated by filtration to obtain 34.0 g (yield: 93%) of a white solid substance.
The target substance can be confirmed by infrared absorption spectrum analysis. Reference example 2 N-(p-perfluorohexenyloxybenzyl)-N-methacryloyloxyethyl-
N,N-dimethylammonium chloride Production of: 2-dimethylaminoethyl methacrylate 7.86
g (0.05 mol) and p-perfluorohexenyloxybenzyl chloride 21.13 g (0.05 mol)
and 0.5g of hydroquinone in 200ml of acetonitrile
ml, and the desired compound can be obtained in the same manner as in Reference Example 1. White solid 27.3g (yield 94%) Reference example 3 1-(p-perfluorononenyloxybenzyl)-4-vinylpyridinium chloride Preparation of: 5.25 g (0.05 mol) of 4-vinylpyridine and 28.63 g (0.05 mol) of p-perfluorononenyloxybenzyl chloride and 0.5 g of hydroquinone
g into 100 ml of acetonitrile, and reacted at 50±5°C with stirring for 0 hour. Most of the reactants precipitate out, but 100ml of benzene is added to the reaction layer.
When the acetonitrile is added, all the small amount of reactants dissolved in the acetonitrile precipitate out. The precipitate was separated by filtration to obtain 30.83 g (yield: 91%) of a pale yellow solid substance. The target compound is confirmed by infrared absorption spectrum analysis. Reference example 4 1-(p-perfluorononenyloxybenzyl)-2-vinylpyridinium chloride Production: 26.43 g of pale yellow solid substance (yield 78%) in the same manner as in Reference Example 3 except that 2-vinylpyridine was used.
is obtained. The target compound is confirmed by infrared absorption spectrum. Reference example 5 N-(p-perfluorononenyloxybenzyl)-N-(3-methacrylamidopropyl)-
N,N-dimethylammonium chloride Preparation of: 7.71 g (0.05 mol) of N-(3-dimethylaminopropyl)methacrylamide and 28.63 g of p-perfluorononenyloxybenzyl chloride
(0.05 mol) and 0.5 g of hydroquinone were added to 200 ml of acetonitrile, and the mixture was reacted and treated in the same manner as in Reference Example 1, resulting in 33.0 g of a pale yellow solid substance.
(Yield 91%) is obtained. The target compound is confirmed by infrared absorption spectrum analysis. Reference Example 6 Production of poly[N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium chloride]: N-(p-perfluorononenyl obtained in Reference Example 1) oxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium chloride (14.59 g (0.02 mol)) and α,α'-azobisisobutyronitrile 0.0493 g (0.0003 mol) were dissolved in 100 ml of isopropyl alcohol, and nitrogen Polymerize with stirring in an atmosphere at 70±5°C for 8 hours. As the polymerization progresses, the polymer begins to precipitate from the solution layer. Removal of the solvent under reduced pressure yields a light brown resinous polymer: 6. Reference Example 7 Production of poly[1-(p-perfluorononenyloxybenzyl)-4-vinylpyridinium chloride]: 1-(p-perfluorononenyloxybenzyl)-4-vinylpyridinium obtained in Reference Example 3 13.56 g (0.02 mol) of chloride and α, α′-
0.0493 g (0.0003 mol) of azobisisobutyronitrile was added to 1,1,2-trifluoro-1,2,2-
Dissolved in a mixed solvent of 50 ml of trichloroethane and 5 ml of isopropyl alcohol and heated at 45°C in a nitrogen atmosphere for 8.
Polymerize with stirring for an hour. The liquid viscosity increases as the polymerization progresses. The solvent is distilled off under reduced pressure to obtain a pale brown resinous substance: 7. Reference Example 8 Production of poly[N-(p-perfluorononenyloxybenzyl)-N-(3-methacrylamidopropyl)-N,N-dimethylammonium chloride]: N-(p- 14.53 g (0.02 mol) of perfluorononenyloxybenzyl)-N-(3-methacrylamidopropyl)-N,N-dimethylammonium chloride and 0.0493 g (0.0003 mol) of α,α'-azobisisobutyronitrile. Dissolve in 100ml of isopropyl alcohol,
Stir polymerization at 70±5°C for 8 hours in a nitrogen atmosphere. As the polymerization progresses, the polymer begins to precipitate from the solution layer. Removal of the solvent under reduced pressure yields a light brown resinous material: 8. Reference Example 9 The monomer obtained in Reference Example 2 was polymerized in the same manner as in Reference Example 6 to obtain poly[N-(p-perfluorohexenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium chloride]. :I got 9. Reference Example 10 The polymer obtained in Reference Example 4 was polymerized in the same manner as in Reference Example 7 to obtain poly[N-(p-perfluorononenyloxybenzyl)-2-pyridinium chloride]:10. Reference Example 11 Production of poly[N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium tetrafluoroborate]: (1) N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium tetrafluoroborate] Nyloxybenzyl)-N-methacryloyloxyethyl-
N,N-dimethylammonium tetrafluoroborate Production: 29.18 g (0.04 mol) of N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium chloride obtained in Reference Example 1 was added to 200 ml of acetonitrile, and tetrafluoro Voreac acid diethyl ether complex
Add another 6.48 g (0.04 mole). This is 1
Stir for an hour. Next, add 100 ml of benzene to the reaction layer and separate the precipitate by filtration. The same procedure was repeated three more times for this precipitate to form a white solid substance 28.12
g (yield 90%). The target substance can be confirmed by infrared absorption spectrum analysis. (2) 15.62 g (0.02 mol) of N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium tetrafluoroborate obtained in (1) and α,α′ -Azobisisobutyronitrile
Dissolve 0.0493g (0.0003mol) in 100ml of isopropyl alcohol, and add 70±5% in a nitrogen atmosphere.
C. for 8 hours with stirring. As the polymerization progresses, the polymer begins to precipitate from the solution layer. Removal of the solvent under reduced pressure yields the target substance, light brown resinous polymer 11. Reference Example 12 Except for using p-perfluorononenyloxybenzyl iodide (0.05 mol) in place of p-perfluorononenyloxybenzyl chloride,
N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium iodide was obtained in the same manner as in Reference Example 1, and this was polymerized in the same manner as in Reference Example 6 to obtain polyester. [N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium iodide]:
Got 12. Reference Example 13 Production of poly[N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium p-toluenesulfonate]: (1) N-(p-perfluoro nonenyloxybenzyl)-N-methacryloyloxyethyl-
N,N-dimethylammonium p-toluenesulfonate Production: 29.18 g (0.04 mol) of N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium chloride obtained in Reference Example 1 was added to 200 ml of acetonitrile, and p- An additional 7.61 g (0.04 mole) of toluene sulfonic acid is added.
Stir this for 1 hour. Next, benzene is added to the reaction layer.
Add 100 ml and separate the precipitate by filtration. This precipitate was subjected to the same operation three more times to obtain 31.16 g (90% yield) of a white solid substance. The target substance can be confirmed by infrared absorption spectrum analysis. (2) 17.31 g (0.02 mol) of N-(p-perfluoronenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium p-toluenesulfonate obtained in (1) and α,α ′-Azobisisobutyronitrile
Dissolve 0.0493g (0.0003mol) in 100ml of isopropyl alcohol, and add 70±5% in a nitrogen atmosphere.
C. for 8 hours with stirring. As the polymerization progresses, the polymer begins to precipitate from the solution layer. When the solvent is removed under reduced pressure, the desired light brown resinous polymer is obtained. Reference example 14 N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,
Production of copolymer of N _- dimethylammonium chloride and n-perfluoroheptylmethyl methacrylate: (1) n-perfluoropeptylmethyl methacrylate _CH2 =C( _CH3 ) _COOCH2 ( _CF2 ) _6CF3 Production: n-perfluoroheptyl methyl alcohol
20.00g (0.05mol), pyridine 5.74g (0.07mol), hydroquinone 0.28g and ether 16.3g
6.27 g (0.06 mol) of methacryloyl chloride was added dropwise to the mixture while stirring at room temperature, and the mixture was further stirred for 3 hours. Next, the precipitate was filtered off, the ether layer was washed three times with water and then dehydrated, and the ether was removed under reduced pressure to obtain 20.59 g (yield: 88%) of a pale brown liquid. (2) N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-
N,N-dimethylammonium chloride 13.13
g (0.018 mol) and 1.46 g (0.0031 mol) of n-perfluoroheptylmethyl methacrylate obtained in (1).
mol) and α,α′-azobisisobutyronitrile 0.0493 g (0.0003 mol) were dissolved in 100 ml of isopropyl alcohol, and the
Polymerize with stirring at ±5°C for 8 hours. As the polymerization progresses, the polymer begins to precipitate from the solution layer. When the solvent is removed under reduced pressure, the desired light brown resinous polymer is obtained. Reference example 15 N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,
N-dimethylammonium chloride and N-(n
Production of copolymer with N-(n-perfluorooctanoate)-N-methacryloyloxyethylmethylamine: (1) N-(n-perfluorooctanoate)-N
-methacryloyloxyethylmethylamine _{CH2 =} C( _CH3 ) _COOCH2CH2N ( _CH3 )CO
(CF ₂ ) ₆ Production of CF ₃ : 2-methylaminoethyl methacrylate 8.59
g (0.06 mol), pyridine 5.74 g (0.07 mol),
0.28 g of hydroquinone was added to 16.3 g of ether, and while stirring at room temperature, 22.43 g (0.05 mol) of n-perfluorooctanoyl chloride was added dropwise, followed by further stirring for 3 hours. Next, the precipitate was filtered off, the ether layer was washed with water three times, and the ether was removed under reduced pressure to obtain 24.98 g of a light brown liquid (yield: 90
%). (2) N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-
N,N-dimethylammonium chloride 13.13
g (0.018 mol), 1.46 g (0.0026 mol) of N-(n-perfluoropeoctanoate)-N-methacryloyloxyethylmethylamine obtained in (1) and α,α′-azobisisobutyronitrile. Dissolve 0.0493g (0.0003mol) in 100ml of isopropyl alcohol, and add 70±
Stir and polymerize at 5°C for 8 hours. As the polymerization progresses, the polymer begins to precipitate from the solution layer. When the solvent is removed under reduced pressure, the desired light brown resinous polymer is obtained. Reference example 16 Poly[N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-N,N-dimethylammonium chloride] and poly[N-(n-perfluorooctanoate)-N-methacryloyl (1) N-(p-perfluorononenyloxybenzyl)-N-methacryloyloxyethyl-
N,N-dimethylammonium chloride 14.59
g (0.02 mol) and 0.0493 g (0.0003 mol) of α,α'-azobisisobutyronitrile were dissolved in 100 ml of isopropyl alcohol and polymerized with stirring at 70±5° C. for 8 hours in a nitrogen atmosphere. As the polymerization progresses, the polymer begins to precipitate from the solution seat. Removal of the solvent under reduced pressure yields a light brown resinous polymer. (2) N-(n-perfluorooctanoate)-N
-methacryloyloxyethylmethylamine
11.10 g (0.02 mol) and 0.0493 g (0.0003 mol) of α,α'-azobisisobutyronitrile are dissolved in 100 ml of isopropyl alcohol and polymerized with stirring at 70±5° C. for 8 hours in a nitrogen atmosphere. As the polymerization progresses, the polymer begins to precipitate from the solution layer. Removal of the solvent under reduced pressure yields a light brown resinous polymer. (3) Thoroughly mix 13.13 g of the polymer obtained in (1) and 1.46 g of the polymer obtained in (2). Reference Example 17 Poly[N-(p-perfluorononenyloxybenzyl)-N- Methacryloyloxyethyl-
N,N-diethylammonium chloride]:17 was obtained. Reference Example 18 Poly[N-(p -perfluorononenyloxybenzyl)-N-(3-methacrylamidoethyl)-N,N-dimethylammonium chloride] I got it. The average degree of polymerization of the polymers produced in Reference Examples 6 to 18 was about 40. Example 1 The quaternary ammonium salt-containing polymer, copolymer and mixture according to the present invention were
1,2-trifluoro-1,2,2-trichloroethane/isopropyl alcohol (10:1 by volume)
The mixed solution is 5 g/solution. Add fibers to this solution
Immerse for 30 seconds, let it drip for 30 seconds, drain the liquid, 120±
After curing at 5° C. for 5 minutes, it is subjected to a water and oil repellency test. The water repellency test is conducted in accordance with JIS L1006 (7.25.2). For the oil repellency test, WhiteMineral Oil (commonly known as Nujol) was used.
and n-Heptane (first class reagent) are shown in the table below. Mix the oil in the appropriate proportions, place several drops (approximately 4 mm in diameter) on two locations on the sample, and judge the penetration state (whether the oil droplets penetrate the cloth) after 3 minutes.

【table】

【table】 The results are shown in Table-1.

[Table] From the above test results, it can be understood that the polymer of the present invention has excellent water and oil repellency.

Claims (1)

[Claims] 1. Quaternary ammonium salt having a perfluoroalkenyl phenyl ether group: [In the formula, R ₁ is hydrogen or a methyl group, R is a perfluorohexenyl group or a perfluorononenyl group, X is a monovalent anion, and n represents an integer of 2 or 3. ] A polymeric water and oil repellent containing as an active ingredient a polymer obtained by addition-polymerizing monomers represented by the following either singly or mutually, or co-addition-polymerizing with other addition-polymerizable monomers.