JPS6323182B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to vinyl esters and methods for producing the same. More specifically, the present invention relates to a vinyl ester as a monomer that provides a polymer that can effectively act as a water and oil repellent, and a method for producing the same. Water and oil repellents made of polymers having perfluoroalkyl groups in their side chains have been known for a long time. For example, in Japanese Patent Publication No. 49-35348, diacetone acrylamide is added to a polymerizable monomer containing a fluoroalkyl group. A water and oil repellent agent made of a copolymer obtained by copolymerizing a compound or its -CH ₂ OR derivative and, if necessary, vinyl chloride, has also been disclosed in Japanese Patent Publication No. 1973-
No. 9416 discloses that methacrylic acid ester having a perfluoroalkyl group at the end of the ester group has
A water and oil repellent agent comprising a copolymer of ethylhexyl methacrylate, a (meth)acrylic acid ester having a hydroxyl group in the ester group, and N-methylolacrylamide is described. These copolymers having perfluoroalkyl groups in their side chains have the specificity of perfluoroalkyl groups, that is, they lack affinity with substances that do not have perfluoroalkyl groups, and they have extremely low surface tension. It is used in water and oil repellents as a copolymer that has improved other required physical properties by copolymerizing it with other comonomers. For example, in the case of the copolymer described in Japanese Patent Publication No. 47-9416, perfluoroalkyl group-containing methacrylic acid ester provides water and oil repellency, 2-ethylhexyl methacrylate provides water repellency and flexibility, and hydroxyl group provides water and oil repellency. The (meth)acrylic acid ester and N-methylolacrylamide contained in the copolymer are copolymerized in order to impart adhesion to fibers and the like to the copolymer. Generally, water and oil repellents are used as treatment agents for fibers, etc., but homopolymers with perfluoroalkyl groups in their side chains are crystalline because the perfluoroalkyl groups are rigid and long chains. ,
When such a crystalline polymer is applied to fibers, etc., the fibers become stiff and their texture is impaired. In addition, since it is a crystalline polymer, if it is applied to colored fabrics, the dried water and oil repellent film will not become transparent and the color of the fabric will be damaged.
In practice, it is never used in the form of a homopolymer. In order to avoid these drawbacks that occur when a homopolymer having a perfluoroalkyl group in the side chain is used for a water and oil repellent, copolymerization with other comonomers as described in the above-mentioned patent publications is necessary. However, even if the modification is successful, the proportion of perfluoroalkyl group-containing monomer components in the copolymer decreases, resulting in In many cases, water and oil repellency, which is the most desired property, is impaired, and to date, there have been almost no water and oil repellents that can satisfy both water and oil repellency and other physical properties at the same time. This is the reality. The present inventor has conducted various studies in search of a polymer that does not take the form of a copolymer that impairs water and oil repellency, but also reduces the rigidity and crystallinity seen in homopolymers. Even if a polymer having a (perfluoroalkylene glycol) group in its side chain is a homopolymer, it does not impair the texture or color when applied to fabrics, etc., and also exhibits sufficient water and oil repellency. I discovered that. Also,
This polymer can be in the form of a copolymer within a range that does not impair its water and oil repellency; in this case, the washing resistance will be even better. The present invention thus provides a vinyl ester as a monomer that provides a polymer that can effectively act as a water and oil repellent, and a method for producing the same. The present invention therefore relates to vinyl esters, which have the general formula (Here, Rf is a perfluoro lower alkyl group, and n is 0 or an integer of 1 to 10.) The present invention also relates to a method for producing a vinyl ester represented by the general formula, wherein the vinyl ester is
general formula (Here, Rf and n are as defined above)
It is produced by subjecting the carboxylic acid represented by the following formula to a lower fatty acid vinyl transesterification reaction. The carboxylic acid represented by the above general formula () can be synthesized by the method described in Japanese Patent Publication No. 10061/1972.
It is carried out by polymerizing hexafluoropropylene oxide in the presence of a catalyst such as cesium fluoride and a solvent such as diglyme or acetonitrile, and hydrolyzing the resulting acid fluoride () in the absence of a catalyst. When hexafluoropropylene oxide is homopolymerized, an acid fluoride represented by the above formula () is obtained, but COF ₂ ,
When CF ₃ COF, C ₂ F ₅ COF, C ₃ F ₇ COF, etc. are used and a polymerization reaction is carried out in the presence of these compounds, polymers containing various perfluoro-lower alkyl groups are produced as shown in the following examples. An acid fluoride is obtained which, upon subsequent hydrolysis, yields the corresponding carboxylic acid. The acid fluoride obtained by polymerizing hexafluoropropylene is a mixture of substances having various numbers of n, and they can be obtained by distillation from n=0 to 1,
It can be separated into fractions 2-3 and 4-6. In addition, by changing the polymerization conditions, it is possible to obtain an acid fluoride having a certain desired number of n. For example, when trying to obtain an acid fluoride with a small number of n, the type of solvent This can be achieved by selecting the desired amount or by increasing the reaction temperature. Specifically, when 100 g of hexafluoropropylene oxide is polymerized at 0°C in the presence of 5 g of cesium fluoride catalyst and 20 ml of acetonitrile, the resulting acid fluoride is a mixture of n = 0 to 4; It can be separated into the following fractions by distillation. n = 0 5.7g n = 1 15.4g n = 2 47.3g n = 3 18.2g n = 4 10.6g The acid fluoride thus obtained may remain a mixture of those having various numbers of n, or The resulting fractions are subjected to a hydrolysis reaction and converted into the corresponding carboxylic acids (). Examples of lower fatty acid vinyl esters used in the transesterification reaction with carboxylic acids include vinyl acetate, vinyl propionate, etc. Vinyl acetate is generally used. In the transesterification reaction, general methods are applied as they are, but for example, lower fatty acid vinyl ester is added in an excess number of moles to the carboxylic acid, and refluxed in the presence of a catalyst such as mercury acetate and concentrated sulfuric acid.
After the reaction is completed, the reaction mixture is neutralized, excess lower fatty acid vinyl ester is distilled off, and the target vinyl ester is then separated by distillation. For the polymerization reaction of the obtained vinyl ester, general radical polymerization techniques can be applied as is. That is, in the case of emulsion polymerization, for example, octadecyldimethylamine hydrochloride is used as an emulsifier.
In addition, azobisisobutyramidine hydrochloride and the like are used as polymerization initiators, and in the case of solution polymerization, aromatic compounds, ketones, alcohols, halogenated hydrocarbons, etc. are used as polymerization solvents, and azobisisobutyronitrile, A peroxide or the like is used as a polymerization initiator to carry out the polymerization reaction. The homopolymer of vinyl ester itself can be used as a water and oil repellent with desired properties, but
It can also be used as a water and oil repellent in the form of a copolymer with other vinyl compounds. Various other vinyl compounds that can be used as comonomers include the following. (1) Vinyl compounds having a hydrocarbon group having 4 or more carbon atoms, such as butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc.; halogen-containing vinyl compounds, such as vinyl chloride, Vinylidene chloride, 2-
Chlorethyl vinyl ether, vinyl bromide, vinyl fluoride, vinylidene fluoride, etc.; diene compounds, such as chloroprene, isoprene, butadiene, etc.: These vinyl compounds or diene compounds are about 99% by weight or less, preferably about 90% by weight or less It is more preferably used in a proportion of about 75% by weight or less, and contributes to improving the flexibility of the polymer and the solubility in halogenated solvents. (2) Vinyl compounds having active groups such as hydroxyl group, amide group, amino group, carboxyl group, phosphoric acid group, sulfonic acid group, etc., such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylolacrylamide, acrylamide , methacrylamide, 4
-Aminostyrene, acrylic acid, methacrylic acid, maleic acid, 2-acryloyloxyethyl acid phosphate, 4-sulfonylstyrene, etc.: These vinyl compounds are present in an amount of about 0.01 to 10% by weight, preferably about 0.05 to 5% by weight. %, more preferably from about 0.1 to 2% by weight, and the presence of active groups in the vinyl compound increases the polymeric fiber,
Strengthens adhesion to paper, leather, etc. (3) Vinyl compounds having a lower perfluoroalkyl group, such as 2,2,2-trifluoroethyl acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl acrylate, etc.: These vinyl compounds is about 10-90% by weight,
Preferably about 20-80% by weight, more preferably about
Used in proportions of 30 to 60% by weight, they further slightly improve the water and oil repellency and flexibility, respectively, of the polymer. Water and oil repellents are prepared in the form of diluted aqueous solutions of polymers synthesized in an aqueous medium by emulsion polymerization or suspension polymerization, or by bulk polymerization. Alternatively, when the solution polymerization method is used, it is carried out in the form of a diluted solution of the organic solvent. Water and oil repellent treatment uses the water and oil repellent prepared in this way to treat various fibers such as cotton, wool, silk, polyester, polyamide, and regenerated cellulose, or woven fabrics made from blends thereof, pulp products, leather, etc. This is done on the objects to be processed. Next, the present invention will be described with reference to examples. Example Carboxylic acid () (Rf
= C ₃ F ₇ , n = 1) 200 g (2.33 mol) of vinyl acetate, 1.6 g of mercury acetate and 0.15 ml of concentrated sulfuric acid were added to 100 g (0.201 mol) of C 3 F 7 , n = 1), and after refluxing for 3 hours, it was neutralized and the excess was removed. Distill vinyl acetate to boiling point 85-105
72.4 g (yield: 69.3%) of a fraction with a temperature of 0.5 mmHg/°C was obtained. Based on the results of NMR spectrum, infrared absorption spectrum, and elemental analysis of this fraction, this fraction is considered to be a compound represented by the following formula. F- _NMR ( _CF3COOH external _standard ): 6-8ppm ( _CF3 , _CF2 ) 55ppm ( _CF3CF2CF2O ) 69.5ppm (CF) H-NMR: 4.5-5ppm and 7-7.5ppm (vinyl (Ester group) Infrared absorption spectrum: 1810cm ^-1 (Ester group) Elemental analysis: Calculated value C: 25.28%, H: 0.19%, F: 61.88% Actual value C: 25.17%, H: 0.45%, F: 61.03% Reference Example 220 parts of deionized water (by weight,
A compound represented by the following formula was obtained by adding 15 parts of trimethyloctadecyl ammonium chloride to (the same applies hereinafter) and using the same method as in the above example. 100 parts, 2-hydroxyethyl acrylate 0.5
1 part, 0.5 part of N-methylol acrylamide and 100 parts of acetone, and thoroughly mixed with a colloid mill and stirred. After the inside of the reactor is sufficiently purged with nitrogen gas, 0.05 part of azodiisobutyramidine hydrochloride as a radical polymerization initiator is added thereto under reflux conditions. After 4 hours, the copolymerization reaction is terminated. A milky white aqueous latex was obtained with a solid content concentration of 23.2% by weight, indicating that the polymerization reaction had proceeded almost completely. Dilute the obtained aqueous latex with water to approximately 0.5
The solid content concentration is adjusted to % by weight, and a cotton cloth is dipped therein. After soaking for about 5 minutes, the cloth was taken out, water was thoroughly squeezed out using a dehydration roll, and then dried at 175° C. for 5 minutes. The cotton cloth thus treated with the copolymer was subjected to a water repellency test, an oil repellency test, a washability test, and a stiffness test as follows. [Water repellency test] A drop of water was dropped onto the treated cotton cloth, and the condition was observed after 5 minutes. Water repellency evaluation condition of water droplets 100 No moisture adhesion is observed on the surface 90 Slight moisture adhesion is observed on the surface 80 Moisture adhesion is observed partially on the surface 70 Moisture is observed on the surface 50 Moisture is observed on the entire surface 0 Complete wetting is observed on both the front and back sides [Oil repellency test] One drop of the test liquid (mixed liquid in the specific proportion shown in the table below) is dropped on the treated cotton cloth, and after 5 minutes have elapsed. Observe the condition. If the dropped test solution is retained on the cloth, test with a test solution with higher n-heptane content, and conversely, if it is not retained on the cloth, test with a test solution with higher n-heptane content. do. Then, using the test liquid that can be retained on the cloth at the limit, the oil repellency is evaluated based on the oil repellency evaluation shown in the table below. In the oil repellency evaluation, the case where 100% Nudyol is retained is 50, and the case where 100% Nudyol is not retained is 0.

[Washability test]

Soaking the treated fabric in water containing 0.1% by weight of neutral chip soap and 0.05% by weight of soda lime;
Stir at 60-80°C for 40 minutes, then press for 30 seconds. After repeating this operation three times, water and oil repellency was evaluated. [Rigidity test] Based on the JISL-1096B method, the stiffness is measured, and then the flexibility is calculated according to the following formula. The closer the softness value is to 1, the closer it is to untreated cloth, and the smaller the value, the harder it is. Softness=bending resistance of untreated fabric/bending resistance of treated fabric The results obtained are shown in the following table. Table test results Water repellency 100 Oil repellency 150 Washing resistance (water repellency) 80 Washing resistance (oil repellency) 130 Softness 0.98 Texture Good

Claims (1)

[Claims] 1. General formula (wherein, Rf is a perfluoro lower alkyl group, and n is 0 or an integer of 1 to 10). 2 General formula (Here, Rf is a perfluoro lower alkyl group, and n is an integer of 0 or 1 to 10.) A general formula characterized by transesterifying a carboxylic acid represented by the following formula with a lower fatty acid vinyl ester: (Here, Rf and n are as defined above)
A method for producing vinyl ester represented by 3. The method for producing a vinyl ester according to claim 2, wherein vinyl acetate is used as the lower fatty acid vinyl ester.