JPH0451543B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to chloromethyl-substituted polyfluoroalkyl esters of polybasic acids, which can be used to treat various substrates such as cloth and paper for the purpose of imparting stain resistance, water repellency, or oil repellency to the substrates. , regarding the use of said compound. The present invention also relates to a method for producing the above compound by reacting an iodine-substituted polyfluoroalkyl ester in its molten state or in a state dissolved or suspended in an inert liquid with elemental chlorine. In recent years, polymers and other compounds containing high-fluorescence segments have been widely used as substances that impart dry stain resistance, oil repellency, or water repellency to textile substrates. A certain degree of resistance of synthetic carpets (such as polyesters, polyamides, polyacrylics) to the dry stains caused by foot traffic is due to the fact that carpets made of synthetic fibers (such as polyesters, polyamides, polyacrylics), such as polymers of perfluoroalkyl acrylates and perfluoroalkyl methacrylates, It is said that this effect is provided by coating with a fluorinated polymer. However, such coated fibers spread fire more easily than uncoated fibers, so
Highly fluorinated monocarboxylic esters and highly fluorinated polycarboxylic esters have been used to impart dry stain resistance and flame resistance. That is a US patent
3923715 and 4029585. U.S. Pat. No. 3,716,401 provides an oil-resistant vinyl surface by adding to the vinyl surface a polymer composition comprising a vinyl polymer dissolved in a volatile solvent and an ester derived from perfluoroethanol and a mono- or polycarboxylic acid. discloses a method for imparting sex and makes it the subject of a patented invention. U.S. Patent No. 3,145,222 discloses a compound having the chemical formula Y(CnF ₂ n)Q, where Y is hydrogen, fluorine, chlorine,
or bromine; n is 1-20 and Q is -
CH ₂ CHIO ₂ CR, −CH ₂ CHI (CH ₂ ) mO
( _CH2 ) _2COOH , -CH=CH( _CH2 )mO
(CH ₂ ) ₂ COOH, −CH ₂ CH ₂ (CH ₂ ) mO
( _CH2 ) _2COOH or -CH=CI( _CH2 )mCOOH
, R is lower alkyl, and m is 0 to 14, and this is the object of the patented invention. Also, the specification is for compounds
Although not intended to be a patent claim for C ₃ F ₇ CH ₂ CHICH ₂ O ₂ CCH ₃ , the compound
discloses C ₃ F ₇ CH ₂ CHICH ₂ O ₂ CCH ₃ and suggests that its hydrolysis and treatment with alkali results in a polyfluoroepoxy polymer intermediate. U.S. Patent No. 4,034,022 is a chemical formula is an isomeric compound having CnF _2o+1 is a fully fluorinated aliphatic chain, n is an integer from 2 to 18, and X and Y are the same group or different groups; Also, each of X and Y is a hydrogen atom, a hydroxy group, an OM group in which M is a metal equivalent, or alkoxy, chloroalkoxy, hydroxypolyalkyleneoxy, or aryloxy, or -
Discloses NZZ' groups in which Z and Z' are the same or different groups, and Z and Z' are each a hydrogen atom or an alkyl, cycloalkyl, or aryl group. These compounds are emulsifiers, foaming agents, leveling agents or rustproofing agents for abrasive or emulsion paints, anticorrosion agents, especially when acid-resistant and oxidation-resistant surfactants are required. It is stated that it can be expected to be used as a solvent evaporation retardant or a hydrophobic agent and an oleophobic agent. The present invention is a chemical formula , wherein Rf is perfluoroalkyl containing 3 to 20 carbon atoms, and R ¹ is citric acid, succinic acid,
It relates to groups derived from chlorendic acid or benzoic acid, benzene dicarboxylic acid or benzene polycarboxylic acid. The present invention also relates to a process for the preparation of the above-mentioned compounds and the use of the above-mentioned compounds for treating textile materials so as to impart dry stain resistance, oil and water repellency to the textile materials. The present invention also relates to a method for treating paper to make it water and oil repellent. Rf is perfluoroalkyl containing 3 to 20 carbon atoms. The compounds of the present invention can be obtained by the reaction illustrated by the formula below. The above reaction follows the following reaction route. Most of the iodine will be present in the final reaction mixture as ICl, but some elemental iodine will also be present. In addition, some ICl ₃ may also be present. The iodine-substituted polyfluoroalkyl ester starting material for the preparation of the compounds of the invention can be obtained by the reaction illustrated by the formula below. A wide variety of allyl esters can be used in accordance with the present invention. In a preferred embodiment, R ¹ is, as described above, a residue obtained by removing a carboxyl group from citric acid, succinic acid, chlorendic acid, benzoic acid, benzene dicarboxylic acid or benzene polycarboxylic acid. Reaction of the iodine-substituted polyfluoroalkyl ester with chlorine can be accomplished by dissolving the iodine-substituted polyfluoroalkyl ester and contacting the molten ester with chlorine, or by suspending or dissolving the iodine-substituted polyfluoroalkyl ester in a suitable liquid. , by reacting with chlorine. A suitable liquid is one that is inert under the reaction conditions. For example, alcohol or water should be avoided as they may react.
Preferred liquids include 1,1,2-trichloro-1,
These include 2,2-trifluoroethane, 1,1,2-tetrachloro-2,2-difluoroethane and tetrachloromethane. It is also possible to use chloroform. All such halogenated carbons function as solvents for the iodine-substituted polyfluoroalkyl ester starting material. Although the liquid medium does not necessarily have to be a solvent for the ester, it is preferable that the liquid medium dissolves at least a portion of the ester. The reaction between the iodine-substituted polyfluoroalkyl ester and chlorine is accompanied by a mild exotherm. The heat generation is slightly larger at the start of the reaction than at the near point of reaction completion. If a solvent is used for the ester starting material, refluxing it provides effective temperature control. There is no critical value for the reaction temperature with chlorine, nor is there a critical value for the pressure. The reaction can be carried out at a temperature between 0° C. and the melting point of the iodine-substituted polyfluoroalkyl ester. Normally, the reaction takes place at approximately 40°C and 55°C when using a solvent.
and when the ester starting material is melted during reaction with chlorine, at temperatures between about 85°C and 90°C. Whether in solution or in the melt, reactions are usually carried out at atmospheric pressure, but
Higher pressures can also be used. Usually, the reaction is carried out until all valence-bonded iodine has been displaced from the ester. Usually, the amount of chlorine is greater than that required to accomplish the above reaction.
A slight excess of chlorine is used. Although there is no harm in introducing chlorine in excess of the amount required to replace all of the iodine in the ester starting material, there is no benefit to the reaction in excess of chlorine. If the R ¹ moiety has some reactivity with chlorine, it may be desirable to avoid using large excesses of chlorine. However, if the R ¹ moiety reacts with chlorine relatively slowly, it may be possible to complete the desired displacement of iodine before a significant amount of chlorine reacts with the R ¹ moiety. After all iodine has been replaced from the ester, it is best to convert the iodine chloride, and if iodine is present, to iodide and chloride ions. For example, water and a soluble salt such as sodium bisulfite can be added for this purpose. The preparation of iodine-substituted polyfluoroalkyl esters is carried out at temperatures ranging between about 50° and 140° C., under pressures between about 1 and 50 atmospheres, and in the presence of free radical chain initiators. If the boiling point of the polyfluoroalkyl iodide or allyl ester used in the reaction is lower than the desired reaction temperature, a pressurized system will be employed. In other cases the reaction may be carried out at atmospheric pressure. The free radical chain initiator may be either an azo compound or a peroxy compound.
For example, α, α′-azobis-(isobutyronitrile); 2,2′-azobis-(2,4-dimethylvaleronitrile); acetyl peroxide; benzoyl peroxide; di-t-butyl peroxide and similar A compound is used. Polyfluoroalkyl iodides can be made by various reactions. For example, by Brace et al.
JACS, 73, 4016 (1951); J.Org by Krespan.
Chem., 23, 2016 (1958); J. by Haszeldine.
Chem.Sor., 1949, 2856, 1952, 4259, 1953,
376; JACS by Hauptschein et al., 79, 2549
(1957). The main uses of the compounds of the present invention are carpets,
Mention may be made of the addition of solutions or aqueous dispersions of the compound to other woven or non-woven fabrics or to paper. Desired properties imparted by the addition of such compounds include water repellency, oil repellency and stain resistance. Achievement of the desired properties is evaluated in different ways for different substrates. For example, in the case of carpet, stain resistance refers to the degree to which the carpet retains its new appearance under normal traffic conditions. Oil and water repellency is also required in carpets so that they can resist stains caused by liquids spilled onto them. In most other end uses, whether the desired effect has been achieved is assessed simply by measuring oil and/or water repellency. The evaluation is 3rd,
The drop test as shown in Tables 4 and 6 or the penetration test as shown in Table 5 may be used. The addition of the novel compound of the present invention from a solution or aqueous dispersion to any of the above substrates deposits on the substrate approximately 0.01% to 1.0% of the novel compound based on the dry weight of the substrate. This may be done by any known method. Preferably, the addition of the novel compounds of the invention is carried out using an aqueous dispersion thereof. An aqueous dispersion of a compound of the invention can be mixed with any polymeric suspension, provided that an amount of the novel compound in the range defined above is deposited on the substrate. For example, the addition of an aqueous suspension of polymethyl methacrylate creates a water-dilutable composition for application to the various substrates contemplated by the present invention. The presence of a polymeric suspension such as aqueous polymethyl methacrylate improves dry stain resistance. Prior to water dilution, such dispersions typically contain about 2% to 20% fluorinated ester and between 2% and 40% dry polymer provided by the suspension. Become. For application to textile substrates such as carpets, the dispersion is further diluted with water. The addition is padding, dispensing,
It may be by any known technique such as spraying or other similar methods. The compounds of the present invention, or compounds of the present invention, including other components, such as poly(methacrylate), are applied to the desired substrate as a solution or dispersion, and then typically dried in water and/or solvents. is removed. Drying is typically carried out by heating to about 120-170°C, although higher or lower temperatures may be used. In particular, heating is preferable in terms of speeding up drying, but drying at room temperature is often sufficient. Furthermore, heat treatment at a temperature higher than that required for drying often improves water and oil repellency. It is believed that such treatment causes at least a portion of the compound of the present invention to melt, which spreads to more effectively coat the substrate. The oil repellency test used herein is the AATCC test method.
118-1978. Oil repellency is defined as the ability of a substrate to resist leakage of oil fluids. In this test method, a droplet of a standard test fluid consisting of a series of selected hydrocarbons of various surface tensions is placed on a substrate and its wetting is observed. Oil repellency grade refers to the highest numbered test liquid that does not leak onto the substrate surface after a period of 30 seconds. Wetting of a substrate surface is usually judged by its darkening at the interface. On black or dark-colored surfaces, wetting can be detected by loss of brightness within the droplet. Standard test solutions are listed in Table 1. Table 1 Standard test liquid oil repellency grade number Composition 1 “Nujiol” 2 “Nujiol” with a volume ratio of 65/35 at 21°C (70〓)/n-hexadecane 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8 n-heptane
Has a Saybolt viscosity of 0.880/at 15℃ (60〓)
A mineral oil having a specific gravity of 0.900, Plough,
Inc. is a trademark. The water repellency test serves as a measure of water resistance and stain resistance; generally, the higher the water resistance grade, the better the stain resistance due to water-based substances. Similar to oil repellency ratings, water repellency ratings refer to the highest numbered test solution that does not wet the substrate surface after a specified period of time, in this case 10 seconds. Standard test solutions are listed in Table 2.

[Table] * Reagent Grade ** Distilled Water According to the test procedure, start with the low number test solution (water repellency grade #1) and carefully place a drop of it in each of three locations on the substrate surface. If two of the three drops still appear spherical or hemispherical after 10 seconds, a drop of the next higher numbered test solution is placed in the adjacent position and observed for 10 seconds. Continue the above procedure until at least 2 or 3 drops of test liquid no longer retain a spherical or hemispherical shape 10 seconds after application. The following examples are given by way of illustration and not as a limitation. Unless otherwise specified, all proportions and percentages are by weight. The temperature is °C and the pressure is mmHg. In some of the examples below, the term MPI is used as an abbreviation for mixed perfluoroalkyl iodides (average n=8) of the formula CnF _2o+1 I having the following composition: n Weight % (approximate value) 4 1-2 6 27-28 8 32-34 10 20-22 12 8-11 14 4-5 16 1-2 >16 Small amount Mixed iodination is not necessarily required for the production of the compounds of the present invention. There is no need to use perfluoroalkyl. It is also possible to use mixed perfluoroalkyl iodides other than those mentioned above. For example, it is possible to use a mixture of the above formula (average n=6) with the following composition: n Weight % (approximate value) 4 3 6 52 8 30 10 11 12 3 14 1 In the following examples, the term ABI is an abbreviation for 2,2'-azobis-(isobutyronitrile). In addition, in these Examples, the term "deoxidation treatment"
means that the treated material was stirred overnight at ambient temperature under a stream of nitrogen, or for at least 1 hour at about 60°C under a stream of nitrogen. In the examples, "nonionic surfactant" means the reaction product of 15 moles of ethylene oxide and 1 mole of a mixture consisting of 1 n-dodecanol, 1 n-tetradecanol and 1 n-hexadecanol. do. "Arch Oud" 18-50 means a 50% aqueous solution of octadecyltrimethyl ammonium chloride. Reference example 1 Production of adduct MPI 146g Triallyl trimellitate 26.4g ABI 1.65g Mix MPI and triallyl trimellitate,
Deoxidized. Then, while maintaining a nitrogen atmosphere, ABI was added in portions over a period of about 24 hours according to the following sequence. Elapsed time (hours) Temperature ABI addition 0 65℃ 0.2g 2-1/3 64℃ 0.2g 3-1/12 67℃ 0.2g 5-5/6 ^* 64-72℃ 0.4g 24 Increased temperature to 99℃ 0.65g Total amount: 1.65g 24-3/4 Reaction completed *The reaction mass was heated to 72°C.
Preparation of dispersions and testing on nylon carpets Adducts 100 g Methyl isobutyl ketone 50 g Arqueous 18-50 6 g Nonionic surfactant 3 g Water Approximately 125 g 2-Methyl-2,4-pentanediol
0.5g Add all ingredients into a mixer at 50-80℃, approx.
Stir for 10 minutes, then twice using a Manton-Gaulin homogenizer [35 Kg/cm ² (500 psi) and 422 Kg/cm ²
(2 stages of 6000 psi)]. Then under reduced pressure approx.
Methyl isobutyl ketone was fractionated with some water using temperatures up to 55°. A portion of the final dispersion was diluted with water and mixed with an aqueous dispersion of acetic acid and polymethyl methacrylate (PMMA). PMMA in dispersion (acetone at 30 °C)
A dispersion consisting of a mixture of adduct, acetic acid, PMMA and water, consisting of particles with an intrinsic viscosity of about 0.7 (0.5 g of PMMA in 100 ml) and an average size of about 0.06 μ, is applied to the surface fibers of the carpet. 0.055% fluorine (in valent bonded form) and 0.186% polymethyl methacrylate based on the weight of the fiber.
A nylon carpet was sprayed onto the surface to receive 0.01% acetic acid and approximately 25% water. The carpet was dried for 30 minutes at 132°C (270°C) in a forced air oven. Carpet samples were tested for oil and water repellency. The sample was also tested for dry stain resistance by placing it in a heavily trafficked hallway with an untreated sample of the same carpet;
The stain resistance was evaluated by comparing this with untreated carpet. The test results for the carpet samples are listed in Table 3. Another portion of the final dispersion was diluted with water and mixed with acetic acid. This was sprayed onto the surface of a nylon carpet, and the surface fibers of the carpet were exposed to 0.055% fluorine (in valently bonded form) and 0.01% acetic acid.
% water was given. The treated carpet was then dried and tested as described above, yielding the data listed in Table 4. Reference Example 2 Production of triallyl citrate adduct MPI 820g triallyl citrate 161g ABI 9.5g MPI and 47ml triallyl citrate were mixed,
Deoxygenated overnight. The next day, the following operations were continued.

[Table] A dispersion of the product of this reference example and a dispersion containing the product of this reference example and polymethyl methacrylate were obtained by the procedure described in Reference Example 1. These divided solutions were added to carpet samples and tested in the same manner as in Reference Example 1, and the results are listed in Tables 3 and 4. Reference Example 3 Conversion from iodide to chloride Iodine-substituted perfluoroalkyl compound represented by the following formula: Using as a raw material, chlorination was carried out in the same manner as in the examples described later to obtain a compound of the following formula. In order to confirm the structure of the product, ¹³ C-NMR (reference material: TMS) was measured for the raw material and the product. Measurements were performed under both (a) non-decoupled conditions and (b) proton noise decoupled conditions. The results are shown in Tables 1 and 2 together with the assignment of each peak determined from the chemical shift.

【table】

[Table] Example 1 In a round bottom flask with a reflux condenser maintained at 0°C, 320 g of the product of Reference Example 1 and 1,1,
120 ml of 2-trichloro-1,2,2-trifluoroethane was added. The mixture was stirred at 48-52°C;
36 g of chlorine gas was introduced below the surface of the liquid over a period of 75 minutes. This mixture was left at room temperature overnight. The next morning, the temperature was maintained in the range 43-52° C. while adding 40 ml of water followed by 140 ml of a saturated aqueous solution of sodium bisulfite. Next, 1,1,2-trichloro-
The temperature was raised to 80°C in order to distill 1,2,2-trifluoroethane. At the same time, 100 ml of methyl isobutyl ketone was added, followed by 147 ml of 20% aqueous sodium hydroxide solution to bring the pH to 5.4. Next, add 120ml of methyl isobutyl ketone and 60g of
_{MgSO4.7H2O was} added. After MgSO ₄ .7H ₂ O was dissolved, the lower aqueous layer was removed using a separatory funnel.
To the organic layer was added 200 ml of a hot aqueous solution of MgSO ₄ .7H ₂ O (saturated at about 60° C.). After stirring well at 80℃,
The lower aqueous layer was discarded. The organic layer was washed with 200 ml of water at 80°C. The product in methyl isobutyl ketone formed the bottom layer. After discarding the upper layer and evaporating the methyl isobutyl ketone portion of the bottom layer, 339g
A residue was obtained. The samples were dried in a vacuum oven to yield 67.5% non-volatile matter. That corresponds to 229 g of dry product, which is 83% of the theoretical yield. The structure of the product is: Here, n is the same as the number given in the definition of MPI. The structure of the product was determined by NMR spectroscopy and confirmed by elemental analysis. According to elemental analysis, n is 8 on average and the following results are obtained. Element calculation value Actual value C 29.8 31.0 H 1.1 1.4 F 57.2 55.7 Cl 6.3 6.1 I 0 0.4 Dispersion liquid production and carpet test Using 352 g of the above methyl isobutyl ketone solution with a solid content of 67.5%, the dispersion liquid was prepared as in Reference Example 1. Prepared as described. Other ingredients are as follows. Water 100ml “Ark Oud” 18-50 18g Nonionic surfactant 73g 2-methyl-2,4-pentanediol
0.5 g homogenization, removal of methyl isobutyl ketone (codispersed with polymethyl methacrylate,
The addition to the carpet (and without the addition of polymethyl methacrylate) and performance tests were carried out as described in Reference Example 1. The test results are listed in Tables 3 and 4. Example 2 Chlorination of the product of reference example 2 500 ml with reflux condenser kept at 0°C
160 g of the product of Reference Example 2 and 60 ml of 1,1,2-trichloro-1,2,2-trifluoroethane were placed in a round bottom flask. The mixture was stirred at 48 DEG-51 DEG C. and 24 g of chlorine gas was introduced subsurface over a period of 75 minutes. Next, 20 ml of water was injected through the condenser, and another 80 ml of a saturated aqueous solution of sodium bisulfite was slowly added. The reflux condenser was then removed and the flask was heated to 84-85°C and held at this temperature for approximately 15 minutes to allow the chlorofluorocarbon to distill off. Next, 90ml of methyl isobutyl ketone was added. The lower aqueous layer was removed via a separatory funnel. The organic layer was washed with 100 ml of hot concentrated magnesium sulfate solution. Isopropanol (50ml) was added to facilitate aqueous layer separation. The weight of the resulting product methyl isobutyl ketone solution was 237 g, and the nonvolatile components were
56.4%, which is 97% of the theoretical yield
This corresponds to 134 g of dry product. The structure of the product determined by NMR spectroscopy and elemental analysis is as follows. The average value of n in MPI used as starting material is 8, so the average empirical formula is C ₃₉ H ₂₀ F ₅₁
It becomes O ₇ Cl ₃ . The dry substance analysis results are as follows. Elemental Calculated Value % Actual Value % C 27.9 28.95 H 1.2 1.2 F 57.9 55.4 Cl 6.3 6.4 I 0 0.4 The above elemental analysis values agree well with the theoretical values and support the above structure. Dispersion Preparation and Carpet Testing A dispersion was prepared as described in Reference Example 1 using 179 g of the methyl isobutyl ketone solution prepared above. Other ingredients were the same as in Reference Example 1 except that methyl isobutyl ketone itself was not added. The dispersion was vacuum distilled to remove the methyl isobutyl ketone, which was applied to a nylon carpet as described above. Test results for treated carpets are listed in Tables 3 and 4. Reference example 4 C ₆ F ₁₃ I 200.7g Triallyl citrate 31.2g Isooctane 31.2g 2,2'-azobis-(isobutylnitrile)
3.3g All of the above ingredients were mixed and deoxidized.
The mixture was then stirred at 67-74°C for 70 minutes and then at 70-75°C for an additional 150 minutes. The first 20 minutes
The reaction is exothermic and (after initial heating to reaction temperature)
Required cooling. Then heating was required again. The volatiles (87 g) were then removed using a rotary evaporator under aspirator vacuum over a steam bath. The volatiles consisted of isooctane (25 g) and penfluorohexyl iodide (62 g). A ratio of 3 moles of perfluoroalkyl iodide was consumed per mole of triallyl citrate, suggesting that the structure of the product was as follows. Analysis of the product by NMR showed that 94% of the allyl double bonds were converted to _-CF2 - _CH2 -CHI- _CH2- structures. The product was dispersed in water and carpet tested as described in Reference Example 1. The results are shown in Tables 3 and 4. Reference Example 5 Production of Adduct MPI 154g Diallyl phthalate 34g ABI 1.7g MPI and diallyl phthalate were mixed and subjected to deoxidation treatment. Then, while maintained in a nitrogen atmosphere,
ABI was added and temperature controlled according to the following procedure. Elapsed time (min) Temperature (°C) ABI addition 0 Heating from 25 0.1g 15 60 15−43 60−68 43 68 0.1g 59 69.5 0.2g 59−85 69−76.5 5 71.5 0.3g 103 71 0.5g 103− 148 69.5-84 148 79 0.5g 212 74.5-100 212 91 Preparation of reaction-completed dispersion and carpet test The procedures described in Reference Example 1 were followed. The results are shown in Table 3. Reference Example 6 MPI 110g Allyl Benzoate 32g ABI 3.55g The procedure was as described in Reference Example 1 with the following order of temperature and ABI addition. Elapsed time (min) Temperature (℃) ABI addition 0 61 0.1g 54 60 0.1g 122 60 0.1g 198 60 0.4g 303 61 0.4g 720 61 Cooling 0 (after rewarming) 56 12 59 0.4g 130 60 Temperature Set control to 71°244 71 0.4g 439 71 0.4g 840 72 Cooling 0 (after rewarming) 56 45 56−80 150 80 1.05g 150−745 80−90 258 minutes to quickly lower temperature to 58°745 90 Completion of Reaction Emulsion production and carpet testing were carried out as described in Reference Example 1. The result is the third
Put it on the table. Example 3 The preparation of the adduct was carried out essentially as described in Reference Example 6. However, C ₈ F ₁₇ I was used instead of MPI, and the adduct was purified by recrystallization from isopropanol. Chlorination of the adduct The equipment is the same as that used in Example 2.
The loaded substances are as follows. (purified) adduct 125 g 1,1,2-trichloro-1,2,2,-trifluoroethane 50 ml Chlorine gas for 2 hours while the contents of the flask are kept between 39° and 55° (15 g) was introduced. Then 20 ml of water was added followed by 80 ml of a saturated aqueous solution of sodium bisulfite. The mixture separated into two layers. This was left for 25 days. The layers were separated and the lower layer was washed with three 200 ml portions of water, at the end of which 10 ml of isopropanol was added. Next, chlorofluorocarbon was heated to 90°-100°C in a vacuum furnace.
evaporated with. The product was a clear amber viscous liquid, weighing 102 g, indicating a 94% yield of the next compound. The product crystallized within one day. The structure was determined by elemental analysis and NMR for both protons and carbon-13.
Determined by spectral analysis. The following results were obtained by elemental analysis. Calculated value % Actual value % C 35.0 34.9 F 52.4 51.7 H 1.6 1.4 Cl 5.8 6.4 I 0.0 0.3 In a 400 ml cylinder lined with Hastelloy C,
10 g of the above product, 10 ml of pyridine and 50 ml of isopropanol were added. The bomb was cooled to about -75°C and vacuumed to about 3 mmHg. Then close the cylinder
Heated to 160°C for 4 hours. The bomb was then cooled. The contents were a homogeneous dark amber liquid. Take out 0.4g of this liquid and make 100ml
of water to give a slightly cloudy solution or suspension. The surface tension of the above solution or suspension was determined to be 22.4 dyne/cm by the ring method using a surface tension meter made by Giunoui. Example 4 In a round bottom flask equipped with an ice-water cooled reflux condenser, 74 g of the product of Reference Example 5 and 1,1,2-
Trichloro-1,2,2-trifluoroethane 30
I put ml. 15 g of chlorine was added subsurface over a period of 53 minutes while maintaining the temperature of the mixture at 51°C. Then add dropwise 40 ml of a saturated aqueous solution of sodium bisulfite, then add enough to bring the pH to about 6 (about 35
ml) of 30% aqueous sodium hydroxide solution was added. Next, the temperature was raised to 85℃ and 1,1,2-trichloro-1,
2,2-trifluoroethane was distilled off. The resulting mixture was transferred to a separatory funnel and 50 ml of methyl isobutyl ketone was added. After shaking this, discard the lower layer and add 50 ml of a saturated aqueous solution of magnesium sulfate to
ml of isopropanol was added and the mixture was shaken again. The lower layer was again discarded and 50ml of hot water was added. After shaking treatment, product solution (lower layer)
I extracted it. The product solution was evaporated under reduced pressure (removal of methyl isobutyl ketone) until the weight of the product solution was 69 g. 57 g of the resulting product was mixed with the following materials. “Ark Oud” 18-50 3g Nonionic surfactant 1.5g 2-methyl-2,4-pentanediol
0.25g Water Approximately 60ml The resulting mixture was stirred well in a mixer, diluted with water, and mixed with acetic acid. This mixture was sprayed onto a nylon carpet so that the surface fibers were provided with 0.055% fluorine (in the form of valence bonds), 0.01% acetic acid and 25% water, based on the weight of the fiber. The carpet was dried and tested as described in Reference Example 1. The test data is listed in Table 4.

【table】

【table】

[Table] Testing of nonwoven fabrics The diluted dispersions tested on nonwoven fabrics are as follows. A The product of Example 1 was dispersed in water as described in Example 1 and the methyl isobutyl ketone was removed also as in Example 1. The product was diluted with water to contain 0.035% fluorine. B The product of Example 2 was treated as in A above to contain 0.035% fluorine. C The product of Example 4 as a 60% solution in methyl isobutyl ketone was dispersed in water as described in Example 2. After distillation of methyl isobutyl ketone, the product was diluted to contain 0.035% fluorine. Non-woven fabric is 60% polyester/40% for operating room wear.
Wood pulp cloth foil was used. Moisture absorption is 193±5%
The diluted dispersion liquid was packed onto a nonwoven fabric so that the following results were obtained. These were then passed twice through a mangle heated to 163°C (325°C). Heating was applied to both sides of the fabric at one time with a contact time of 75 seconds with the mangle. Add the treated cloth foil along with the untreated sample.
It was subjected to the DART (U.S. Disposables Association's recommended test method) 80.9 test. In this test, the fabric foil samples were cut to the size of standard food storage bin double lid discs. A 1 quart (0.95) airtight food storage bottle was charged with 600 ml of 0.9% NaCl aqueous solution, the disk was clamped to the top of the bottle, and the bottle was inverted. Water disc penetration times were recorded as described in Table 5. Table 5 Diluted dispersion used Penetration time A > 60 minutes B 31 minutes C 5 minutes None Immediate Kraft paper test The treatment dispersion used is of the same type as described under "Nonwoven fabric test". However, the concentration is different. Weight 0.49g/cm ² (20b/100ft ² )
138+2% Claremont unbleached kraft paper is packed with the liquid shown below.
of moisture absorption. The paper was then passed twice through a mangle at 104°C (220°C) to dry both sides at once. The contact time with the mangle was 75 seconds. The treated paper and the comparative untreated paper were subjected to AATCC oil repellency testing. The results are shown in Table 6.

[Table] Example 5 Chlorination of triallyl trimellistate adduct without solvent Product of Reference Example 1 984g Chlorine 117g Saturated aqueous sodium bisulfite solution 290ml 30% aqueous sodium hydroxide solution 455ml Mantle heater and finger-shaped cooler for water cooling with faucet Reference Example 1 was placed in a 3 round bottom flask with a bottom drain port.
of product (984 g) was charged. The flask was flushed with nitrogen while the contents were heated to melt at 85°C.
While stirring the contents of the flask, chlorine gas was introduced below the liquid surface in the following order.

Table: Stirring was stopped and the mixture was cooled to room temperature and left overnight. The next morning, the mixture was heated to 70°C and the upper aqueous layer was removed with a siphon. Water (400ml) and 490ml
of methyl isobutyl ketone was added and the mixture was heated to 55-68°C with stirring. Stirring was stopped and the upper aqueous layer was extracted with a siphon. Add water (400 ml preheated to 75-80°C) and heat the mixture to 70°-80°C.
Stir for 15 minutes. Stirring was stopped and the lower organic layer was drained. Its weight was 1245g. The sample was dried in a vacuum oven at 90-100°C for 1 hour. Non-volatile matter is 64.7%, 806g product, 95% yield
corresponds to NMR analysis (by proton signal) of the vacuum dried product confirmed that it was exactly the same as the product of Example 1. Example 6 Chlorination of sodium citrate without solvent 399.6 g of the product of Reference Example 2 45 g of chlorine 210 ml of saturated aqueous sodium bisulfite solution 105 ml of 30% aqueous sodium hydroxide solution A round bottom flask with a bottom drain port was used. . A mantle heater (Glas-Col) was used for heating. The product of Reference Example 2 was charged to a flask at room temperature and melted under nitrogen. Next, in accordance with the following sequence, chlorine gas was introduced below the liquid surface while stirring the contents of the flask. Elapsed time (minutes) Temperature (℃) Operation and notes 0 83 Start of Cl ₂ introduction 20 85 11 g of Cl ₂ introduced 50 83 29 g of Cl ₂ introduced 78 83 After introducing 45 g of Cl ₂ , Cl ₂ introduction stopped, cleaning with N ₂ Start 100 83 Addition of 200 ml H ₂ O 101 58 Reheat to 80-85 °C 110 81 Start addition of NaHSO ₃ solution 125 84 End addition of NaHSO ₃ solution 130 83 Start addition of NaOH solution 160 End addition of NaOH solution 170 85 PH = 3.5 This At this point, stirring was stopped and the upper aqueous layer was drawn out using a siphon. Then 300ml of water was added and the mixture was reheated to 88°C with stirring. Stop stirring;
The molten product (330 g) was drained from the bottom of the flask. A sample of the product was dried in a vacuum oven at 100°C and had a non-volatile content of 95%. This is the theoretical yield
It is 91%. The results of elemental analysis are as follows. Element Calculated Value% Actual Value% C 27.9 31.62 Cl 6.3 6.4 F 57.9 56.6 H 1.2 0.98 I 0.0 0.76 The results of NMR (proton) and elemental analysis indicate that the product has the same structure as the product of Example 2. It is shown that. Example 7 Preparation of MPI/diallyl isophthalate (DAIP) adduct MPI 8655 g DAIP 1980 g ABI 60 g In a round bottom flask mounted in a temperature controlled water bath.
The total amount of MPI was charged. Add 600ml DAIP,
The mixture was deoxygenated. The mixture was heated to 72±3° C. and the reaction was carried out according to the addition order below. Elapsed time (min) ABI addition (g) DAIP addition (ml) 0 6 58 200 60 6 89 200 118 200 120 6 17 200 180 6 238 200 240 6 298 Remaining 300 6 360 6 420 6 480 6 540 6 1410 76℃ 1410-1450 Gradually raise the temperature to 82℃ to melt the product 1485 Chlorination of the reacted adduct Place the above adduct (4000 g ) and 1,1,2-
Trichloro-1,2,2-trifluoroethane (2775 g) was charged and heated to about 40° C. until the contents were stirrable. The temperature was maintained between 35° and 50°C, during which time chlorine was added subsurface over a period of 3.5 hours, followed by 1 part of water. It took 2.5 hours,
2200 ml of saturated aqueous sodium bisulfite solution was added at a temperature range of 32-50°C. A 30% aqueous sodium hydroxide solution was added while cooling to maintain the temperature in the range between 30° and 50°C. After 1.5 hours, PH is 5.4
The addition of the sodium hydroxide aqueous solution was terminated when the amount reached. The amount of sodium hydroxide aqueous solution used is
It was 1865ml. During the addition of the sodium hydroxide solution, some salt formed inside the neck of the flask. 1 of water was used to periodically rinse the salt from the neck of the flask. The mixture was allowed to stand for 0.5 hour before the top aqueous layer was removed. Water (2900ml) and 1,1,
2-Trichloro-1,2,2-trifluoromethane (250ml) and isopropanol (250ml) were added and the mixture was stirred and allowed to stand. A product solution of chlorofluorocarbon (light amber solution) was withdrawn from the bottom of the flask. The solid content of a product weighing 5352 g (by drying in a vacuum oven at 90-100°C) is 57.4
It was %. This corresponds to 3072 g of product, 83.6% yield. The product solution is a very pale amber liquid. The structure identified by NMR is as follows.

Claims (1)

[Scope of Claims] 1 Rf is perfluoroalkyl containing 4 to 16 carbon atoms, and R ¹ is a group derived from citric acid, succinic acid, chlorendic acid, or benzoic acid, benzene dicarboxylic acid or benzene polycarboxylic acid. and n is a number from 1 to 4: a reactant compound having the formula: A method for producing a target compound having 2. The method according to claim 1, comprising:
How R ¹ is derived from citric acid. 3. The method according to claim 1, comprising:
A method in which R ¹ is derived from o-phthalic acid. 4. The method according to claim 1, comprising:
A method in which R ¹ is derived from isophthalic acid. 5. The method according to claim 1, comprising:
How R ¹ is derived from trimellitic acid. 6. The method according to claim 1, comprising:
A method in which R ¹ is derived from pyromellitic acid. 7. The method according to any one of claims 1 to 6, wherein Rf contains 6 to 8 carbon atoms.