JPS6029724B2 - Method for producing a polymer with excellent water and oil repellency - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer with excellent twill water and oil repellency, and more specifically, the present invention relates to a method for producing a polymer having excellent twill water and oil repellency. The present invention relates to a method for producing a polymer with excellent water and oil repellency, which comprises polymerizing a specific ester mixture containing:

Conventionally, homopolymers of polymerizable compounds containing fluoroalkyl groups, such as acrylates or methacrylates containing perfluoroalkyl groups, or polymerization thereof with acrylic acid esters, maleic anhydride, chloroprene, butadiene, and methyl vinyl ketone have been used. Water and oil repellent agents made of copolymers with the compounds obtained are known.

Various methods for producing fluoroalkyl group-containing polymerizable compounds have also been proposed. For example, a method for producing polyfluoroalkyl acrylate or polyfluoroalkyl methacrylate by reacting a polyfluoroalkyl iodide with an alkali metal salt of an unsaturated carboxylic acid (see Japanese Patent Publication No. 39-18112, etc.), or a method for producing a polyfluoroalkyl iodide with an alkali metal salt of an unsaturated carboxylic acid (see Japanese Patent Publication No. 39-18112, etc.); A method using a transesterification reaction of an unsaturated carboxylic acid with a lower alkyl ester (eg, methyl acrylate, methyl methacrylate, etc.) has been proposed. In the proposed method, the formula CH2=CRIC
Acrylates or methacrylates containing a fluoroalkyl group represented by OORRf (in the formula, Rf is a polyfluoroalkyl group, R is an alkylene group, and RI is a hydrogen atom or a methyl group) are obtained, and these have water and oil repellency. It is used as a raw material for producing polymers. The method described in Japanese Patent Publication No. 39-18112 uses a polyfluoroalkyl iodide, which is advantageous in terms of the process, but it is important to suppress the by-product of olefins containing fluoroalkyl groups due to the dehydrohalogenation reaction. This is Inranga. In addition, according to the transesterification reaction, the fluoroalkyl group-containing acrylate or methacrylate of the above formula can be obtained with good selectivity. Generally, in the production of alkyl acrylates or methacrylates, esterification reactions between alcohols and acrylic acid or methacrylic acids and transesterification reactions between alcohols and acrylic esters or methacrylic esters are considered, but in the previous esterification reaction, Since the yield of the target product is low, the latter transesterification reaction is usually adopted.

From this point of view, transesterification has generally been used to produce methacrylates from fluoroalkyl group-containing acrylates. As a result of conducting studies on the esterification reaction of polyfluoroalcohols with acrylic acid or methacrylic acid, the applicant has come to the following fact.

That is, Rf - R - OH alcohol and C ratio = CRIC
According to the esterification reaction with the unsaturated carboxylic acid OOH, the selectivity of the acrylate or methacrylate CQ = CRICOORRf remains at about 90% at most, suppressing the production of other created substances at a rate of 5 to 30%. admitted that it is difficult to do so. In addition, the 5 to 30%
It has been found that the derivatives of degrees are compounds containing a fluoroalkyl group and are polymerizable, and that acrylates or methacrylates mixed with the derivatives can be used as a raw material for the production of water and oil repellent agents. Ta. Furthermore, CH2
When using acrylate or methacrylate (=CRICOORRf) as a raw material for producing a water-repellent and oil-repellent polymer as a mixture with a by-product, compared to the case where CH2=CRICOORRf without contamination by the above-mentioned by-product is used. It was newly discovered that it is possible to produce a twill water repellent with superior performance. For example, JP-A-49-86
See Publication No. 487, etc. As a result of further consideration of the above facts, the present inventor found that useful by-products have the formula CH2
-CRICOOCH2CHRICOORRf (However,
It was confirmed that Rf, R, and RI in the formula are the gestal compound (as described above).

According to the research and examination of the present inventor, it has been found that the raw material unsaturated carboxylic acid contains the formula CH2=CRICOOCH2CH in advance.
It has been found that by generating an unsaturated acid dimer called RICOOH, it is possible to more easily and advantageously synthesize an ester mixture containing a useful gester compound by reaction with a polyfluoroalcohol.
For example, unsaturated carboxylic acid as a raw material may dimerize during storage or distillation, and those containing an appropriate amount of such unsaturated acid dimer can be effectively used as a raw material in the present invention. Available for use. Thus, the present invention has been completed based on the above findings, and
Formula CH2 = CRICOOCH2CHRICOOH (
However, RI in the formula represents a hydrogen atom or a methyl group) containing an unsaturated acid dimer represented by 30% by weight or less. unsaturated carboxylic acid with the formula RmOH (wherein Rf is a linear or branched polyfluoroalkyl group having 3 to 2 solid carbon atoms, and R is a straight chain polyfluoroalkyl group having 1 to 10 carbon atoms). (represents a chain or branched alkylene group)
The formula CH2=CRICOOCH2CH obtained by reacting with a polyfluoroalcohol represented by
A gestal compound of RICOORRf (in which Rf, R, and RI are as described above) and a compound of the formula CH2=CRIC
A method for producing a polymer with excellent water and oil repellency, characterized by polymerizing a polyfluoroalkyl group-containing ester mixture containing a monoester compound OORRf (in which Rf, R, and RI are as described above) This is a new offering.

In the present invention, the polyfluoroalcohol and unsaturated carboxylic acid as raw materials for the esterification reaction are not particularly limited as long as they are represented by the above formula, and various types can be used.

Unsaturated carboxylic acids of formula CH2=CRICOOH include acrylic acid with C ratio=CHCOOH and CH2=C(C
H3) There is methacrylic acid on the COO day. For polyfluoroalcohols of the formula RfROH, Rf is a C3-C polyfluoroalkyl group and R is a C, to C,o alkylene group, but preferably Rf is a C3-C,5, especially C6-C , 2 perfluoroalkyl group, R is C2-C
4 is an alkylene group. As polyfluoroalcohols, those expressed by RfCQC day 20 are:
It is particularly preferably employed from the viewpoint of ease of acquisition and other aspects.

In the present invention, as the raw material unsaturated carboxylic acid, formula C
It is important to use a mixture containing less than 3% by weight of the unsaturated acid dimer H2=CRICOOCH2CHRICOOH. If the content of such unsaturated acid dimer is too large, it will be disadvantageous to the smooth and favorable reaction with polyfluoroalcohol, and the water repellency of the polymer obtained from the formed ester mixture will be reduced. The basic performance of the device will deteriorate. Furthermore, if the content of unsaturated acid dimer is too small, it will be difficult to achieve the effect of incorporating a useful gestal compound, and it will be difficult to achieve the desired gestal compound mixing rate through reaction with polyfluoroalcohol. Special conditions will be required. Therefore, it is usually preferable to employ an unsaturated carboxylic acid containing an unsaturated acid dimer in an amount of 5 to 3% by weight, preferably 10 to 25% by weight. In the present invention, there is no particular reason to limit the method for obtaining the unsaturated carboxylic acid containing the unsaturated acid dimer, and the dimer obtained by another synthesis reaction is added to and mixed with the raw material unsaturated carboxylic acid. However, in a preferred embodiment, unsaturated acid dimers are preferably formed and contained in a desired proportion by irradiating the raw unsaturated carboxylic acid with ultraviolet light.

The reaction molar ratio of the polyfluoroalcohol and the unsaturated carboxylic acid mixture during the esterification reaction in the present invention is not particularly limited; ~20
It can be selected from a wide range of moles.

Usually a reaction molar ratio of 1 to 5 moles, preferably 1 to 2 moles of polyfluoroalcohol per mole of unsaturated carboxylic acid mixture may be employed. Therefore, it is recognized that for the water-repellent oil-based polymer of the present invention, the content of the specific gester compound in the ester mixture is about 5 to 30%, preferably about 10 to 25%. It is being

If the content of the gestal compound is too high, the basic performance of the obtained polymer as a water and oil repellent agent will be degraded. Furthermore, if the content of the diester compound is too small, no effect will be observed due to its inclusion. The desired content ratio of the gester compound (a) can be easily achieved within the range of the reaction molar ratio during the esterification reaction. Conditions during the esterification reaction in the present invention,
There is no particular reason to limit the operating means, devices, etc., and they can be adopted over a wide range.

The reaction temperature is usually about 60 to 13,000, preferably about 7 to 90 oo, and the reaction pressure is about normal pressure, and reduced pressure, autogenous pressure, increased pressure, etc. are also suitable. The esterification reaction can also be carried out by employing various polymerization inhibiting means, such as introducing oxygen or adding a polymerization inhibitor such as hydroquinone. A polymerization inhibitor may be added to the raw material unsaturated carboxylic acid mixture and introduced into the reaction system, or the polymerization inhibitor may be added to the reflux when the reaction is carried out under reflux. The esterification reaction in the present invention is an equilibrium reaction, and can be made to proceed in a desired direction by separating and removing by-product water from the reaction system. Therefore,
It is desirable to adopt conditions and operations that allow by-product water to be separated and removed from the reaction system. For example, 0.3 to 5 times the weight of polyfluoroalcohol, preferably 0.5 to 1.
For example, water can be removed by azeotroping (69q0) by adding 5 tones of benzene. Moreover, the esterification reaction in the present invention can also be carried out in the presence of a suitable catalyst.

For example, strong inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, sulfonic acids,
It is preferable to use 0.01 to 0.1 mol of organic strong acids such as carboxylic acids, metal alkoxides such as aluminum and titanium, etc. per 1 mol of polyfluoroalcohol.
Furthermore, it goes without saying that the esterification reaction of the present invention can be carried out in various modes such as batchwise, semi-continuous, and continuous. The polyfluoroalkyl group-containing ester mixture thus obtained is purified as necessary and then used as a raw material for the polymerization reaction.

For example, when an equal amount of water or a dilute aqueous sodium carbonate solution is added to the reaction product and the rope is allowed to rise, the excess unsaturated carboxylic acid mixture and catalyst move to the upper aqueous layer, and the molester and gester compounds in the lower layer. etc. can be separated. Accordingly, in the present invention, the polyfluoroalkyl group-containing ester mixture described above is polymerized to obtain a polymer having twill water and oil repellency.

Usually, in addition to the above mixtures, ethylene, pinyl acetate, vinyl chloride, vinyl fluoride, vinylidene halides, acrylonitrile, methacrylonitrile, styrene, d-methylstyrene, p-methylstyrene, acrylic acid and its alkyl esters, methacryl Acids and their alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, methylolated diacetone acrylamide,
One or two types of polymerizable compounds that do not contain fluoroalkyl groups, such as N-methylol acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, glycidyl acrylate, and maleic anhydride. It is also possible to copolymerize the above as constituent units of a polymer. By copolymerizing these polymerizable compounds that do not contain fluoroalkyl groups, in addition to shark water and oil repellency, various properties such as stain resistance, dry cleaning resistance, washing resistance, selective solubility, flexibility, and texture can be achieved. It is possible to appropriately improve the properties of In order to obtain the polymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, and various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be used. can also be adopted.

For example, a method may be employed in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant or the like and then copolymerized under the conditions of a rope. As a polymerization initiation source, various polymerization initiators such as organic peroxides, azo compounds, persulfates, and further ionizing radiation such as Y-rays can be employed. Furthermore, as a surfactant, almost all of the various anionic, cationic, or nonionic emulsifiers can be used. Therefore, the raw material polymerizable compound may be dissolved in a suitable organic solvent and subjected to solution polymerization by the action of a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. soluble in the organic solvent used). I can do it. Suitable solvents for solution polymerization include trichlorotrifluoroethane, tetrachlorodifluoroethane, methylchloroform, and the like. Aerosol type, organic solvent type or latex type water and oil repellent agents can be directly produced by solution polymerization method or emulsion polymerization method. The water- and oil-repellent polymer of the present invention thus obtained is prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method.

For example, as mentioned above, an aqueous emulsion can be prepared directly by emulsion polymerization, or a solvent solution type can be prepared directly by solution polymerization. For solvent solution type polymers, polymers obtained by other polymerization methods such as bulk polymerization or emulsion polymerization can be used in acetone, methyl ethyl ketone, diethyl ether, dioxane, methyl chloroform, trichloroethylene, tetrachloroethylene, tetrachlorodifluoroethane, trichloroethylene, etc. They may also be prepared by dissolving them in one or a mixture of suitable organic solvents, such as salt fluorinated saturated hydrocarbons such as trifluoroethane. For the aerosol type, prepare a solution type solvent solution as described above, and add dichlorodifluoromethane, monofluorotrichloromethane,
A propellant such as dichlorotetrafluoroethane may be added and the mixture may be filled into a suitable container. The water- and oil-repellent polymer of the present invention can be applied to the article to be treated by any method depending on the type of the article and the preparation form (solvent solution type, aerosol type, etc.).

For example, in the case of an aqueous emulsion or a solvent solution type, a method may be employed in which the coating is applied to the surface of the treated object by a known coating method such as dip coating and then dried. Further, if necessary, it may be applied together with a suitable crosslinking agent to perform curing. In the case of an aerosol-type water-repellent and oil-repellent agent, it is sufficient to simply spray the material onto the object to be treated, and it dries immediately to exhibit sufficient water-repellent and oil-repellent properties. Furthermore, the water repellent agent of the present invention may be prepared by mixing the fluoroalkyl group-containing polymer with other polymer blenders, such as other water repellent agents, oil repellent agents, insect repellents, repellents, and antistatic agents. Of course, it is also possible to add and use appropriate additives such as dye stabilizers, anti-wrinkle agents, etc. There are various examples of articles that can be treated with the water repellent oil agent of the present invention without any particular limitation.

Examples include textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces and plaster. Then,
Examples of textiles include natural fibers of animal and plant origin such as cotton, hemp, wool, and silk; various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; Examples include inorganic fibers such as glass fibers and asbestos fibers, and woven fabrics of mixed fibers thereof. Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention.

Vertical water resistance and oil repellency shown in the following examples are shown on the following scale. That is, the twill water quality is JISL-10
Water repellency N○ by spray method of 05 (see Table 1 below)
The oil repellency is determined by placing several drops of the test solution shown in Table 2 below (approximately 4 skins in diameter) on two locations on the sample cloth, and determining the penetration state after three days of tochi sand. (AATCC-TMI
18-1966) Table 1, Table 2. Furthermore, Ayamizu sexual relations. Vertical oily shaft. Those marked with a 10 mark indicate slightly better performance.

Examples 1-3C8F. 7CH2C melon OH232 evening (0
．． 5 moles), 10.2 moles of P-toluene sulfonic acid, predetermined amounts of acrylic acid and acrylic acid dimer (see Table 3),
170 tons of benzene and 0.4 tons of hydroquinone were charged into a four-necked flask equipped with a distillation column, and reacted for 80 tons for 6 hours. Water produced during the reaction was azeotroped with benzene and removed by distillation (distillation column top temperature 69 qo). After the reaction was completed, residual benzene was removed by vacuum distillation. Add 3 parts of soda to the reaction mixture.
The washing liquid and oil layer were weighed using a 0% aqueous solution and analyzed using a gas chromatograph.

C8F,7CH2CH20 day conversion rate, C8F,7CH2CH20COCH C
H2 and C8F, 7CH2CH20COCH2
Table 3 shows the selectivity of port OCOCH=CH2. Using the mixture of fluoroalkyl group-containing polymerizable compounds thus synthesized, a water-repellent and oil-repellent polymer was synthesized under the following polymerization conditions. Polymerization conditions Fluoromonomer: 7.5 evenings Polymerization temperature: 65 qo Vinyl chloride: 2.0 evenings Polymerization time: 1
The polymer solution obtained under the above polymerization conditions was dissolved in a mixed solvent of methyl chloroform and trichlorotrifluoroethane (
The mixture was diluted to a solid content concentration of 0.5% using a mixing ratio of 50/50.

A cotton broadcloth was immersed in this diluted solution with sand of No. 1, the solution was thoroughly shaken off, the cloth was air-dried for 3 hours, and the water resistance and oil repellency were measured. The measurement results are shown in Table 4. Table 3 Table 4 Comparative Examples 1-2 The same esterification reaction as in Examples 1-3 was carried out using the specified amounts of acrylic acid and acrylic acid dimer (Table 5),
The results are shown in Table 5.

Furthermore, the water repellency of the polymer obtained under the polymerization conditions of the same machine,
Twill oiliness was measured in a similar manner. The results are shown in Table 6. Comparative Example 3 C8F, 7CH2CH 20 days 232 evenings (0.5 mol),
11.5 moles of P-toluenesulfonic acid, 215 moles of methyl acrylate (2.5 mol), and 0.4 moles of hydroquinone were charged into a four-necked flask equipped with a distillation column, and reacted at 80 ml for 6 hours.

Methanol produced during the reaction was mixed with methyl acrylate and removed by distillation. After the reaction was completed, remaining methyl acrylate was removed by vacuum distillation. The reaction mixture was thoroughly washed with a 3% aqueous sodium carbonate solution, and the lower oil layer was separated and weighed, and analyzed by gas chromatography. The conversion rate of C8F,7CH2C5OH is 98%, C8F,7CH2CH20COCH=C
The selectivity of H2 is 99%, C8F, 7CH2CH20CO
No formation of CH2C ratio OCOCH=CH2 was observed. Using this fluoromonomer, the water repellency and oil repellency of the polymers obtained under the same polymerization conditions as in Examples 1 to 3 were measured in the same manner as in Examples 1 to 3. The measurement results are shown in Table 6 below. Table 5 Table 6 Example 4 CnF2n + ICH2CH 20 days (n=6, 8, 10,
12 is 1:3:2:1) 254.5 units (0.5 mol),
P-toluenesulfonic acid 10.2 hours, acrylic acid 38.
0 mole (0.48 mol), acrylic acid dimer 19.0 mole (
0.12 pm) was esterified in the same manner as above.

The results were that the alcohol conversion rate was 97.5%, the selectivity was C2n0, C2d40COCH = C was 74.9
%, C cape 2n+, C2 day 40COCH2CH20C
OCH=CH223.0%.

Polymerized in the same manner as above and measured as water repellency 100
Oil repellency was 7.

Claims (1)

[Claims] 1 Formula CH_2=CR^1COOCH_2CHR^1C
The formula CH_2=CR^1COOH (however, R^1 in the formula contains 30% by weight or less of an unsaturated acid dimer represented by OOH (however, R^1 in the formula represents a hydrogen atom or a methyl group) 1 is as described above) and an unsaturated carboxylic acid represented by the formula RfROH (wherein Rf is a linear or branched polyfluoroalkyl group having 3 to 20 carbon atoms,
R represents a linear or branched alkylene group having 1 to 10 carbon atoms), which is obtained by reacting a polyfluoroalcohol represented by the formula CH_2=C
R^1COOCH_2CHR^1COORRf (However,
Rf, R, R^1 in the formula are as described above) and a diester compound of the formula CH_2=CR^1COORRf (however,
A method for producing a polymer with excellent water and oil repellency, characterized by polymerizing a polyfluoroalkyl group-containing ester mixture containing a monoester compound (in which Rf, R, R^1 are as described above). 2. The manufacturing method according to claim 1, wherein the concentration of the diester compound in the ester mixture to be polymerized is 5 to 30% by weight. 3. The manufacturing method according to claim 1, wherein the concentration of the monoester compound in the ester mixture to be polymerized is 70 to 95% by weight. 4. The manufacturing method according to claim 1, wherein an unsaturated carboxylic acid containing 5 to 30% by weight of unsaturated acid dimer is used. 5. The manufacturing method according to claim 1, wherein an alcohol containing a perfluoroalkyl group having 3 or more carbon atoms is used as the polyfluoroalcohol. 6. The process according to claim 1, wherein a reaction molar ratio of 1 to 5 moles of polyfluoroalcohol per mole of unsaturated carboxylic acid mixture is employed. 7. The manufacturing method according to claim 1, wherein the reaction between the unsaturated carboxylic acid mixture and the polyfluoroalcohol is carried out at a temperature of 60 to 130°C.