DK162979B - POLYFLUORAL COOLESTERS, THEIR PREPARATION AND USE - Google Patents

Description

DK 162979 B

The invention relates to chloromethyl-substituted polyfluoroalkyl esters of polybasic acids and their use in the treatment of a variety of materials, such as textile products and paper, for the purpose of imparting resistance to the materials and water and oil repellent properties. The invention also relates to a process for the preparation of the compounds of this invention in which iodine-substituted polyfluoroalkyl esters are reacted with elemental chlorine, the iodine-substituted esters being in the molten state 10 or dissolved or suspended in an inert liquid.

In recent years, polymers and other compounds containing high-fluorinated segments have been widely used to impart resistance to dry soiling as well as oil and water repellent properties for textile materials. A certain degree of resistance to dry, traffic-caused soiling in carpets made from synthetic fibers (such as polyesters, polyamides and polyacrylic compounds) is said to be provided by fluoropolymer coatings, e.g. polymers of perfluoroalkyl acrylates and methacrylates. As such coated fibers can support the progressive movement of a flame lighter than an uncoated fiber, high-fluorinated mono- and polycarboxylic acid esters have been used to provide resistance to dry dirt and combustion resistance, cf. U.S. Patent Nos. 3,923,715 and 4,029,585.

Polymers of perfluoroalkylethyl (meth) acrylates, i.e.

acrylates or methacrylates, are used in large quantities commercially as water, oil and dirt repellent, e.g. for rainwear. These (meth) acrylates are prepared by a method consisting of the following five main steps: (1) reacting perfluoroalkyl iodides with ethyl one to form perfluoroalkylethyl iodides, (2) reacting the perfluoroalkylethyl iodides with sulfur trioxide (in the form of oleum) to form perfluoroalkylethyl sulfates, (3) reacting the perfluoroalkylethyl sulfates with water to

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2) forming perfluoroalkylethyl alcohols, (4) reacting the perfluoroalkylethyl alcohols with a (meth) acrylic acid or an ester or halide thereof to form perfluoroalkylethyl (methyl) acrylates, and 5 (5) polymerizing the perfluoroalkylethyl (meth) acrylates.

The aforementioned novel polyfluoroalkyl esters of the general formula set forth below have water, oil and dirt repellent properties comparable to those of the prior art polymers mentioned above. Furthermore, the compounds of the invention, which thus constitute practical alternatives to the known compounds, can be prepared according to the invention by a method which is substantially simpler and far less difficult to regulate than the known method mentioned above: thus chlorine with an iodine-substituted polyfluoroalkyl ester, thereby replacing the iodine with chlorine, at the same time a rearrangement takes place. The fluorine-containing starting material for preparing the polyfluoroalkyl esters is the same as the perfluoroalkyl iodides used in the prior art for reaction with ethylene, cf. step (1) above. Thus, from the perfluoroalkyl iodide, according to the invention, it is only necessary to carry out at most two chemical conversions to prepare the compounds of this invention.

In contrast, as noted above, it is necessary to perform no less than five chemical conversions to prepare the poly [perfluoroalkylethyl (meth) acrylates] of the prior art from the same perfluoroalkyl iodide.

Furthermore, the sulfation step (2) and hydrolysis step (3) of the known five-step method are significant sources of difficulties in this method. In the sulfation step, molten iodine is typically added to 65% oleum. During this addition, considerable foaming takes place due to the viscous nature of the pulp, the very strong exothermic reaction that takes place, the formation of the low boiling by-product sulfur dioxide and the fact that the reaction temperature lies

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3 near the boiling point of the sulfur trioxide content of the oleum used. Foam formation reduces the efficiency of stirring and this leads to higher local temperatures and excess sulfur trioxide, and both of these conditions favor an increase in the formation of undesirable by-products. The foaming also reduces the heat transfer efficiency resulting in longer processing time. In the hydrolysis step, the viscous sulfating mass containing approx. 30-38% free sulfur trioxide, 10 to water at atmospheric pressure, resulting in a vigorous exothermic reaction. Thus, spraying takes place at the surface, whereby insoluble materials are introduced into the acid scrubber used in connection with the equipment used. In addition, 2-perfluoroalkylethyl hydrate gels are formed which cause decreased surface stirring and cause local heat concentrations leading to further severe spraying. The reduced stirring also results in intermittent thermal shocks, which has a devastating effect on the glass-lined equipment used.

U.S. Patent No. 3,716,401 discloses a method of rendering a vinyl surface resistant to oil by applying to the surface of a polymeric material containing a vinyl polymer dissolved in a volatile solvent and an ester derived from perfluoroethanol and a mono- or Polycarboxylic acid.

In U.S. Patent No. 3,1345,222, compounds of formula y (cnF2n) Q 'wherein Y is hydrogen, fluorine, chlorine or bromine, n is a number from 1 to 20, and Q is -CH2CHIO2CR, -CH- CHI (CH ~) O (CHO) o CO_H, -CH = CH (CH.J O (CH_) o CO, H, 2 2 m 222 2 m 222 30 -CH-CH- (CH 2) 0 (CH-) CO_H or -CH = CI (CH2 COOH, where R is 222m222 2 m 2 lower alkyl and m is a number from 0 to 14. Although the patent does not otherwise disclose such a compound, the compound of formula C And it is stated that it can be hydrolyzed and treated with alkali to form a polyfluoro epoxy polymer intermediate.

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In U.S. Patent No. 4,034,022, isomers of the formulas / C F_ in -CHC1-CH - O-P-X n 2n + 1,2 v

5 Y

/ ° C F.-CH-O-P-X n 2n + l v

New ch2ci

10 where cnF2n + 1 is a Per 1-unorated aliphatic chain, n is an integer from 2 to 18, and X and Y are the same or different and each represents a halogen atom, a hydroxyl group, the group OM where M is a metal equivalent or an alkoxy, chloroalkoxy, hydroxypolyalkyleneoxy, aryloxy or -NZZ 'group wherein Z

15 and Z * are the same or different and each represents a hydrogen atom or an alkyl, cycloalkyl or aryl group. It is stated that the compounds are believed to be useful as emulsifying or foaming agents, especially when a tensioactive agent resistant to acids and oxidants is required, as polish or emulsifying agents for polish or emulsion paints, as corrosion inhibitors, solvent evaporation retardants or as hydrophobic and oleophobic agents.

The invention relates to compounds of the general formula 25 Γ ol R-CH, CHOC-R1

f 2I

CH 2 Cl 1 n in which R f is a fluorinated aliphatic group containing r 1 at least 3 C atoms, R is an optionally substituted alkyl, aryl, alkenyl, aralkyl, cycloalkyl or cycloalkenyl group, and n is a number from 1 to 4, preferably from 2 to 4.

The invention also relates to a process for the preparation of the compounds of this invention and to a process for preparing the compounds of the invention.

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for using the compounds for treating textile materials so as to confer resistance to dry soiling and oil and water repellent properties. The invention further relates to a method of treating paper to render it repellent to water and oil.

is a saturated, monovalent, non-aromatic aliphatic group. The chain may be straight, branched or cyclic and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms. A fully fluorinated group is preferred, but hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic group, provided that no more than one atom of each is present in the group for every two carbon atoms and that the group at least must contain a terminal perfluoromethyl group. In a preferred embodiment, the fluorinated aliphatic group does not contain more than 20 C atoms because such a large group results in ineffective utilization of the fluorine content.

In a more preferred embodiment, R 1 is a perfluoroalkyl group containing from 3 to 20 C atoms.

The compounds of the invention can be prepared by the reaction shown in the following equation: r 01 r 01

RfCH2CHCH2OC- R1 + Clj— <► RfCH2CH0C— R1 + ICl

I I

and I CH-Cl „25 L_ * -In · - 2 Jn

However, while most of the iodine will be present in the final reaction mixture in the form of IC1, some elemental iodine will be present. Furthermore, there may be some IC13 to 30 present. The iodine-substituted polyfluoroalkyl ester starting material for the preparation of the compounds of this invention can be prepared by the reaction shown in the following reaction scheme: RfI + CH2 = CHCH2OC-R1 - «- Rf CHjCHCHjOC - R1 __ J n L 1 _Jn

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According to the invention, a wide variety of alkyl esters can be used. In a preferred embodiment, R 1 is alkyl, aryl, aralkyl or cycloalkyl. Thus, e.g. be the residue remaining after esterification of citric acid, phthalic acid 5 (o-, m- or p-isomer), benzoic acid, succinic acid, chlorendic acid (chlorendic acid) or benzene polycarboxylic acids, for example trimellitic acid or pyromellitic acid.

The reaction between the iodine-substituted polyfluoroalkyl ester and chlorine can be accomplished by melting the iodine-substituted polyfluoroalkyl ester, on which this molten ester is brought into contact with chlorine, or the iodine-substituted polyfluoroalkyl ester can be suspended or dissolved and dissolved in chlorine. A suitable liquid is inert under the reaction conditions. For example, alcohols and water should be avoided as they are expected to react. The preferred liquids include 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1,2-tetrachloro-2,2-difluoroethane and tetrachloromethane. It is also possible to use chloroform. All such halohydrocarbons act as solvents for the iodine-substituted polyfluoroalkyl ester starting material. Although it is not necessary for the liquid medium to be a solvent for this ester, it is preferred that the ester is at least partially soluble in the liquid medium.

The reaction of the iodo-substituted polyfluoroalkyl ester 25 with chlorine is mildly exothermic, being somewhat more exothermic at the beginning of the reaction than at a point near its end. When a solvent is used for the ester starting material, reflux thereof provides an effective control of the exotherm's reaction. The temperature of the reaction with chlorine is not critical, and so is the pressure. The reaction can be carried out at a temperature between 0 ° C and the melting point of the iodine-substituted polyfluoroalkyl ester. Usually, the reaction is carried out at a temperature between ca. 40 and approx. 55 ° C when using a solvent, and at between ca. 85 and approx.

At 90 ° C when the ester starting material is melted during the reaction with chlorine. Although the reaction, whether it takes place in solution

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or in molten form, usually carried out at atmospheric pressure, however, elevated pressures may be used as well. Normally, the reaction is allowed to proceed until substantially all of the covalently bound iodine has been displaced from the ester.

Normally, a small excess of chlorine is used relative to that required to satisfy the reaction equation shown above. The introduction of chlorine in excess of the amount required to displace all the iodine in the ester material will not do any harm, but such excess in the middle will also not promote the turnover. However, if the R 2 moiety tends to react with chlorine, it may be desirable to avoid a large excess of chlorine. Thus, if the R 2 moiety reacts relatively slowly with chlorine, it may be possible to complete the desired iodine exchange completely before a substantial amount of chlorine reacts with the R 2 moiety.

After all the iodine has been displaced from the ester, it is best to convert the iodine chloride or chlorides and optionally iodine to iodide and chloride ions. For example, water and a soluble salt such as sodium bisulfite may be added for this purpose.

The preparation of the iodo-substituted polyfluoroalkyl ester is carried out in the presence of a free radical initiator at temperatures ranging from 50 and approx. 140 ° C and at pressures between approx. 1 and approx. 50 atmospheres. If the polyfluoroalkyl iodide or allyl ester used for this reaction has a boiling point below the desired reaction temperature, a pressure system is used. Otherwise, the reaction can be carried out at atmospheric pressure.

The free radical initiator may be either an azo compound or a peroxy compound, e.g. α, α'-azo-bis (isobutyronitrile), 2,2'-azo-bis- (2,4-dimethylvaleronitrile), acetyl peroxide, benzoyl peroxide or di-tert.butyl peroxide.

The polyfluoroalkyl iodides can be prepared by a variety of reactions, cf. eg. Brace et al., JACS, 73, 4016 (1951), Krespan, J. Org. Chem., 2B, 2016 (1958), Haszeldine, 35 j. chem. Soc., 1949, 2856 and 1952, 4259 as well as 1953, 376 and Hauptschein et al., JACS, 79, 2549 (1957).

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The principle application of the compounds of the invention comprises applying solutions or aqueous dispersions of the compounds in question to carpets, other woven or nonwoven textile materials, or paper. The desired properties disclosed in the application of said compounds include water repellent properties, oil repellent properties, and dirt resistance. The degree to which these desirable properties are obtained is assessed differently for the various materials.

In the case of e.g. carpets make the resistance to dry soiling a measure of the carpet's ability to maintain its new appearance under normal conditions of carpeting. In addition, oil and water-repellent properties are required for rugs to provide stain resistance from spilled liquids.

In most of the other final applications, the desired effects are judged simply by measuring oil and / or water repellent properties. This can be done by drop tests as indicated in Tables III, IV and VI, or by penetration as indicated in Table V.

Application of the novel compounds of the invention from solution or aqueous dispersion to any of the above materials can be carried out in any known manner so as to deposit on the material from ca. 0.01 to approx.

25 1.0% of the novel compound, based on the dry weight of the material. Preferably, the application of the compounds of this invention is effected from an aqueous dispersion. Provided that quantities of the new compounds in the above range are applied to the material, the aqueous dispersions of the compounds of the invention can be mixed with an aqueous polymer suspension. For example, the addition of an aqueous suspension of polymethyl methacrylate provides a composition which can be diluted with water for application to the various materials herein. The presence of the polymer suspension, e.g. an aqueous polymethyl methacrylate suspension improves the resistance to dry soiling. Such dispersion will before

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9 thinning with water usually contain from approx. 2 to approx. 20% fluorinated ester according to the invention and between approx. 2 and approx. 40% of the polymer, calculated on a dry basis, and obtained by means of said suspension. For use in textile materials, e.g. blankets, the above dispersion is further diluted with water. The application or application may be in any known manner, e.g. by dipping or exhaust spraying.

After one or more compounds of the invention, as a solution or dispersion and optionally containing other ingredients such as poly (methyl methacrylate), have been applied to the desired material, this is usually dried to remove water and / or solvent. Normally, the drying is done by heating to approx. 120 to approx. 170 ° C, although higher or lower temperatures can be used. In particular, drying at ambient temperature is often sufficient, although heating is usually preferred to speed drying. It has been found that such treatment at least in part causes melting of the composition of the invention to spread and cover the material more effectively.

The oil repellent properties test used here is an adapted AATCC Test Method 118-1978. Oil repellent action is defined as the ability of a material to withstand wetting with 25 oily liquids. According to the test method, droplets of standard test liquids consisting of a selected series of hydrocarbons having varying surface stresses are applied to the material and the wetting is observed. The rating for the oil repellent effect is the highest numbered test liquid that does not moisten the surface of the material over a period of 30 seconds. Wetting of the surface is usually seen by a darkening thereof at the interface. On black or dark surfaces, wetting can be observed by a loss of "sparkling" within the droplet. The standard test fluids used are listed in Table I.

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Table I

The standard test liquids

oil Rejection

Evaluation Composition 5 1 "Nujol" 2 65/35 "Nujol" / n-hexa-

decane by volume at 21 ° C

3 n-hexadecane 4 n-tetradecane 10 5 n-dodecane 6 n-decane 7 n-octane 8 n-heptane 15 "Nujol" is a trademark of Plow, Inc., for a mineral oil having a Saybolt viscosity of 360/390 at 38 ° C and a density of 0.880 / 0.900 at 15 ° C.

The water repellency test provides an index of aqueous stain resistance, since generally the higher the water repellency rating, the better the resistance to staining with water-based substances. Like the oil rejection rating, the water rejection rating is the highest numbered test liquid that does not wet the surface of the material over a specified time, in this case 10 seconds. The standard 25 test solutions are those listed in Table II.

30 o

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Table II

Standard test solutions

Flash point

Water Rejection Composition

5 Rate of ice% Isopropanol% H20x C ° F

1 2 98 2 5 95 50 122 3 10 90 40 104 4 20 80 28 82 10 5 30 70 19 66 x reagent quality,% by volume xx distilled 15 In accordance with the test procedure, start with the lowest numbered test liquid (water rejection rating no. 1) and carefully apply a drop thereof at each of three locations on the surface of the material. If after 10 seconds two of the three drops are still visible in spherical or hemispherical form, 20 drops of the next, higher numbered test liquid are placed on an adjacent area and these are observed for 10 seconds. This procedure is continued until at least two or three drops of the test liquid cease to be spherical or hemispherical after application.

The following examples serve to illustrate the invention. Unless otherwise indicated, all parts and percentages are by weight. Temperatures are given in degrees centigrade and pressure is given in mm Hg.

In some of the following examples, the term "MPI" 30 is used to abbreviate "Mixed Perfluoroalkyl Iodides" of the formula C F ~ ..I having the following composition (through-n ^ n + in section n = 8): 35

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n Weight% (approximate) 4 1-2 6 27-28 8 32-34 5 10 20-22 12 8-11 14 4-5 16 1-2> 16 small amounts 10

It is not necessary that mixed perfluoroalkyl iodides be used in the preparation of the compounds of the present invention. Furthermore, mixed perfluoroalkyl iodides other than the above may be used, e.g. a mixture of the above formula having the following composition (average n = 6): n Weight% (approximate), 4 3 6 52 20 8 30 10 11 12 3 14 1 25 In the following examples, the term "ABI" is an abbreviation In addition, in these examples, the term "deoxygenated" means that the material so treated is stirred overnight at ambient temperature under a stream of nitrogen, or stirred for at least 30 hours at about 30 ° C for 2,2'-azo-bis (isobutyronitrile). 60 ° C under a stream of nitrogen In examples ne "nonionic surfactant" means the reaction product of 15 moles of ethylene oxide with 1 mole of a mixture of n-do-decanol-1, n-tetradecanol-1 and n-hexadecanol "Arquad 18-50" means a 50% solution of octadecyl trimethyl ammonium chloride in water.

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Example 1

Preparation of adduct MPI 146 g

Triallyl trimellite 26.4 g of ABI 1.65 g of MPI and triallyl trimellite are mixed and deoxygenated.

Maintaining a nitrogen atmosphere, then ABI is added portionwise over a 24 hour period following the following schedule: 10 Elapsed Time (hours) Temperature ABI Addition 0 65 ° C 0.2 g 2- 1/3 64 ° C 0, 2 g 3- 1/12 67 ° C 0.2 g 15 5-5 / 6 * 64-72 ° C 0.4 g 24 raised to 0.65 g

99 ° C

total 1.65 g 24-3 / 4 reaction completed 20 v

The reaction mass is heated so that the temperature is increased to 72 ° C.

Preparation of dispersion and testing on nylon carpet Adduct 100 g 25 Methyl isobutyl ketone 50 g Arquar 18-50 6 g

Non-ionic surfactant 3 g

Water approx. 125 g of 2-methyl-2,4-pentadiol 0.5 g of 30

All ingredients are combined at 50-80 ° C in a mixer, stirred therein for approx. 10 minutes and then passed twice through a Manton-Gaulin homogenizer (2 steps: 35 kg / cm and 420 kg / cm). The methyl isobutyl ketone is then distilled off with some water, using a partial vacuum and temperatures up to approx. 55 ° C.

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A portion of the finished dispersion is diluted with water and mixed with acetic acid and an aqueous dispersion of polymethyl methacrylate (PMMA). PMMA in the dispersion has an inherent viscosity of approx. 0.7 (0.5 g of PMMA in 100 ml of acetone at 5 30 ° C) and consists of particles having an average size of approx. 0.06 µl. The mixed dispersion containing the adduct, acetic acid, PMMA and water is then sprayed onto the surface of a nylon blanket so that the surface fibers of the blanket receive 0.055% fluorine (in covalently bonded form), 0.186% polymethyl methacrylate, 0.01% acetic acid, and ca. 25% H2 O, based on the fiber weight. The blanket is dried for 30 minutes in a forced air oven at approx. 132 ° C. Carpet samples are tested for oil and water repellency. Samples are also tested for resistance to dry soiling by placing them in a heavily trafficked hall along with untreated specimens of the same rug, judging for soiling resistance in comparison to the untreated rug. The results of the blanket tests are shown in Table III.

Another portion of the finished dispersion is diluted with 20 water and mixed with acetic acid. The mixture is then sprayed onto the surface of a nylon blanket so that its surface fibers receive 0.055% fluorine (in covalently bonded form), 0.01% acetic acid and approx. 25% water. The treated blanket is then dried and tested as described above to give the results given in Table IV.

Example 2

Preparation of Triallyl Citrate Adduct MPI 820 g 30 Triallyl Citrate 161 g ABI 9.5 g MPI and 47 ml triallyl citrate are mixed and deoxygenated overnight. The following day is the following work schedule: 35

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Elapsed time Temperature ABl additive. Triallylcitrattilsætn. (rain) (° C) (g) _ (ml) _ 0 25 (heating) 0/5 30 64 5 45 62 5 70 65 20 88 65 10 96 64 10 125 66 15 10 146 71 1.0 158 72 residue 158-270 72-91 330 81 2.0 375 81 2.0 15 414 81 4, 0 441 81 stopped overnight (cold time not included) 441-486 88-100 486 95 reaction completed 20

Dispersions of the product of this example, with or without polymethyl methacrylate, are prepared by the methods set forth in Example 1. Separate portions thereof are applied to carpet samples and tested as in Example 1 and the results appear from Tables III and IV.

EXAMPLE 3 In a round bottom flask equipped with a reflux condenser maintained at 0 ° C, 320 g of the product of Examples 1 and 120 ml of 1,2,2-trichloro-1,2,2-trichloromethane are applied. fluoro-ethane. The mixture is stirred at 48-52 ° C and 36 g of chlorine gas is introduced under the surface of the liquid over a period of 75 minutes.

This mixture is left at room temperature overnight. The next morning, the temperature is kept in the range of 43-52 ° C while adding 40 ml of water and then 140 ml of a saturated aqueous solution of

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sodium bisulfite. The temperature is raised to 80 ° C to distill off the 1,2,2-trichloro-1,2,2-trifluoroethane. At the same temperature, 100 ml of methyl isobutyl ketone is added, followed by ca. 147 ml of 20% aqueous sodium hydroxide solution to adjust the pH to 5.4. Then 120 ml of methyl isobutyl ketone and 60 g of MgSO 4, 7 H2 O are added, and after the latter has dissolved, the lower aqueous layer is removed in a separatory funnel. To the organic layer is added 200 ml of a hot aqueous solution of MgSO 4, 7 h 2 O (saturated at about 60 ° C).

After thorough mixing at 80 ° C, the lower aqueous layer is discarded. The organic layer is washed with 200 ml of water at 80 ° C and the product in methyl isobutyl ketone forms the bottom layer. The upper layer is discarded and, after evaporation of a portion of the methyl isobutyl ketone in the bottom layer, 339 g of residue are obtained. A sample 15 thereof is dried in a vacuum oven and found to be 67.5% non-volatile. This corresponds to 229 g of dry product, which is 83% of the theoretical yield.

The product has the following structure: n CH? C1

20 I

c-o-c-CH2-cnF2n + 1 ^ gVC-O- | -CH2-CnF2n + 1 o CH2C1 C-O-C-CH2-CnF2n + 1

25 11 I

0 CH 2 Cl 1 where n is as given in the definition of MPI. The structure of the product is determined by NMR spectroscopy and supported by elemental analysis. The latter gives the following results for n with a 30 average value of 8:

Elemental Calculated,% Found,% C 29.7 31.0 H 1.2 1.4 F 57.1 55 35 Cl 6.3 6.1 I 0.4

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Preparation of dispersion and testing on pins

A dispersion is prepared as described in Example 1 using 352 g of the above described methyl isobutyl ketone solution containing 67.5% solids. The other components are as follows:

Water 100 ml "Arquad" 18-50 18 g

Non-ionic surfactant 73 g of 2-Methyl-2,4-pentanediol 0.5 g Tables III and IV.

Example 4

Chlorination of the product of Example 2 In a 500 ml round bottom flask equipped with a reflux condenser held at 0 ° C, 160 g of the product of Example 2 and 60 ml of 1,1,2-trichloro-20 are placed. , 2,2-trifluoroethane. The mixture is stirred at 48-51 ° C and 24 g of chlorine gas is introduced below the surface over a period of approx. 75 minutes. Then, 20 ml of water is poured through the condenser, followed by 80 ml of a saturated aqueous solution of sodium bisulfite, which is slowly added. The reflux condenser is then removed and the flask is heated to 84-85 ° C and held at this temperature for approx. 15 minutes for distillation of the chlorofluorocarbon. Next, 90 ml of methyl isobutyl ketone is added. The aqueous lower layer is removed by means of a separating funnel and the organic layer is washed with 30 100 ml of hot concentrated magnesium sulfate solution. Add 50 ml of isopropanol to facilitate separation of the aqueous phase. The final wash is performed with 100 ml of water to which is added 20 ml of isopropanol. The resulting solution of the product in methyl isobutyl ketone weighs 237 g and is 56.4% non-volatile, corresponding to 134 g of dry product. The yield is 97% of the theoretical.

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The structure of the product as determined by NMR spectroscopy and elemental analysis is as follows: 0 CH2Cl CH2-C- ° -C-CH2-cnF2n + 15 o CH2Cl H0-CCOC-CH2-CnF2n + 110 CH2Cl -CH2-cnF2n + in 10 The average value of nine MPI used as the starting material is 8 and the average empirical formula is therefore ^ gH ^ Fg ^ O ^ Clg · The dried material is analyzed as follows:

Elemental Calculated,% Found,% 15 C 28.0 28.95 H 1.0 1.2 F 57.9 55.4

Cl 6.4 6.4 I 0 0.4 20 The foregoing elemental analysis shows satisfactory agreement with the theoretical values and supports the correctness of the structure given above.

Preparation of the dispersion and testing on carpet 25 The dispersion is prepared as described in Example 1 using 179 g of the methylisobutyl ketone solution prepared above. The other ingredients are as described in Example 1, except that no methyl isobutyl ketone is added as such. The dispersion is distilled off under vacuum to remove the methyl isobutyl ketone and applied to a nylon blanket as previously described. The results of the test of the treated carpet are shown in Tables III and IV.

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Example 5 C6F13I 200.7 g

Triallyl citrate 31.2 g

Isooctane 31.2 g 5,2,2-azo-bis- (isobutyronitrile) 3.3 g

All of the above ingredients are combined and deoxygenated. Then the mixture is stirred at 67-74 ° C for 70 minutes, followed by 150 minutes at 70-75 ° C and then 80 minutes at 79-83 ° C. For the first 20 minutes of the time, the reaction is exothermic and requires cooling (after initial heating to obtain reaction temperature). Later, heating is again required.

87 g of volatiles are then removed on a aspirator vacuum steam bath using a rotary evaporator.

The volatiles consist of 25 g of isooctane and 62 g of perfluorohexyl iodide. Thus, three mold parts of perfluoroalkyl iodide are consumed per liter. mole of triallyl citrate, indicating that the product structure is as follows:

0 I

2 (, ch2-c-o-ch2-ch-ch2-c6f13

o I

HO-CC-O-CH2-CH-CH2-C6F13 I °) CH2-C-O-CH2-CH-CH2-C6F13 25 Examination of the product by nuclear magnetic resonance shows that 94% of the allyl double bonds have been converted to the following structural element: -CF2-CH2-CHI-CH2-.

The product is dispersed in water and tested on a blanket as described in Example 1. The results are shown in Tables III and IV.

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Example 6

Preparation of adduct MPI 154 g

Diallylphthalate 34 g 5 ABI 1.7g MPI and the diallylphthalate are mixed and deoxygenated. Maintaining a nitrogen atmosphere, ABI is then added and the temperature adjusted according to the following scheme: 10 Elapsed time (min.) Temperature (° C) ABI addition 0 heating from 25 0.1 g 15 60 15-43 60- 68 43 68 0.1 g 15 59 69.5 0.2 g 59-85 69-76.5 85 71.5 0.3 g 103 71 0.5 g 103-148 69.5-84 20 148 79 0 , 5 g 212 74.5-100 212 91 reaction completed

Preparation of Carpet Dispersion and Testing 25 This is carried out as described in Example 1 and the results are shown in Table III.

Example 7

Preparation of adduct 30 MPI 110 g

Allyl benzoate 32 g ABI 3.55 g

Proceed as described in Example 6, using the following scheme for the temperature and addition of ABI: 35

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Elapsed time (min.) Temperature (° C) ABI addition O 61 0.1 g 54 60 0.1 g 122 60 0.1 g 5 198 60 0.4 g 303 61 0.4 g 720 61 cooled O ( after reheating) 56 12 59 0.4 g 10 130 60 ten temperature control, reset

to 71 ° C

244 71 0.4 g 439 71 0.4 g 840 72 cooled 15 (after reheating) 56 45 56-80 150 80 1.05 g

150-745 80-90 briefly chilled to 58 ° C

at 258 min.

745 90 reaction completed 20

The preparation of emulsion and blanket testing is carried out as described in Example 1 and the results are shown in Table III.

Example 8

The preparation of the adduct is carried out essentially as described in Example 7, but with the following exceptions: MPI is replaced with CgF II and the adduct is purified by recrystallization from isopropanol.

30

Chlorination of adduct

The same equipment is used as in Example 4 and the following materials are charged:

Adduct (purified) 125 g 35 l, 1,2-Trichloro-1,2,2-trifluoroethane 50 ml

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15 g of chlorine gas is introduced over two hours, keeping the flask content at a temperature between 39 and 55 ° C. Then 20 ml of water is added, followed by 80 ml of a saturated aqueous solution of sodium bisulfite. The mixture is separated into two layers and allowed to stand for 25 days.

The layers are separated and the lower layer is washed with three 200 ml portions of water, adding to the last 10 ml of isopropanol. The chlorofluorocarbon is then evaporated in a vacuum oven at 90-100 ° C. The product is a clear, amber and viscous liquid and weighs 102 g, which corresponds to 94% yield of: C8F17 "CH2" CH ~ CH2 "C1 0 15 0 = C- <0)

The product crystallizes within a day. The structure is determined by elemental analysis and NMR spectroscopy, both proton and carbon-13. The elemental analysis gives the following results: 20 Calculated,% Found,% C 35.0 34.9 F 52.4 51.7 H 1.6 1.4

Cl 5.8 6.4 25 I 0.0 0.3

To a 400 ml bomb lined with Hastelloy C is added 10 g of the above product, 10 ml of pyridine and 50 ml of isopropanol. The bomb is cooled vigorously to approx. -75 ° C and evacuated to a pressure of approx. 3 mm Hg. Next, the bomb is closed and heated to 160 ° C for 4 hours. The bomb is then cooled. The contents are a homogeneous, dark amber liquid. 0.4 g of this liquid is taken out, which is mixed with 100 ml of water to give a relatively cloudy solution or suspension. This solution or suspension has a surface tension of 22.4 dynes per day. cm, measured by the ring method using a Du Nouy tensiometer.

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Example 9 In a round bottom flask equipped with an ice-water cooled reflux condenser 74 g of the product of Example 6 and 30 ml of 1,1,2-trichloro-1,2,2-trifluoroethane are placed.

5 The mixture is maintained at 51 ° C while 15 g of chlorine is applied below the surface over 53 minutes. Next, 40 ml of a saturated aqueous solution of sodium bisulfite is added dropwise, followed by sufficient 30% aqueous sodium hydroxide solution to adjust the pH to approx. 6 (ca.

35 ml). The temperature is then raised to 85 ° C to distill off 1,1,2-trichloro-1,2,2-trifluoroethane. The resulting mixture is transferred to a separatory funnel and 50 ml of methyl isobutyl ketone is added. After shaking, the lower layer is discarded and 50 ml of a saturated aqueous solution of magnesium sulfate and 20 ml of isopropanol is added and the mixture is shaken again.

Discard the lower layer again and add 50 ml of warm water. After shaking, dissolve the product (lower layer).

The product solution is evaporated in vacuo (removal of methylisobutyl ketone) until it weighs 69 g. 57 g of the resulting product are mixed with: "Arquad" 18-50 3 g

Non-ionic surfactant 1.5 g 2-Methyl-2,4-pentanediol 0.25 g 25 Water approx. 60 ml

The resulting mixture is stirred thoroughly in a mixer, then diluted with water and mixed with acetic acid. This mixture is sprayed onto a nylon blanket so that the surface fibers receive 0.055% fluorine (in covalently bonded form), 0.01% acetic acid and 25% water, based on the fiber weight. The blanket is dried and tested as described in Example 1. The obtained test data are shown in Table IV.

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Table III (with PMMA)

Resistance to Oil

Ex. No. Dry Dirt Rejection Water Rejection 1 N-C (a) 5 5 5 2 C-M (a) 5 5 3 N-C 5 6 4 M 5-65 5 N-C (a ^ 5 5 6 C 5 5 10 7 N O 3

ubeh. taps - O O

Degree of superiority over untreated carpet E = same N = noticeably better 15

C = significantly better M = much better (a) = 0.11% PMMA

Table IV (without PMMA) 20 Oil resistance

Ex. no ♦ dry contamination rejection Water rejection 1 N-C 5 5 2 C 5 5 3 SX 5 5 25 4 N 5 5 5 MW * X 4 5 9 M 3-45 x S = slightly better MW = much poorer wv

Tests on nonwoven materials

The diluted dispersions tested on nonwoven materials are as follows: 35 A. The product of Example 3, dispersed in water as described in Example 3, and having methyl isobutyl ketone removed as

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25 described in said example. This product is diluted with water to a content of fluorine of 0.035%.

B. The product of Example 4, treated as described under A to a content of 0.035% fluorine.

The product of Example 9 in the form of a 60% solution in methyl isobutyl ketone is dispersed in water as described in Example 4. After distillation of methyl isobutyl ketone, the dispersion is diluted to a fluorine content of 0.035%.

The nonwoven material is a 60% polyester / 40% wood-10 pulp material intended for use in operating room apparel. The diluted dispersions are dipped onto the nonwoven + material to obtain a wet absorbance of 193-5%. They are then dried by being passed twice through a deficiency apparatus heated to ca. 163 ° C, the heat being applied once on each side of the material, using a contact time in the 75 seconds deflector.

The treated materials as well as an untreated sample are subjected to the DART-Disposables Association Recommended Test (DART-80.9), whereby a sample of the material is cut to 20 the size of a slice of a standard two-piece preservative lid.

A preservative glass with a capacity of approx. Charge 0.95 liters with 600 ml of water containing 0.9% NaCl. The dial attaches to the top of the glass and this is turned upside down. The time taken to penetrate the disc is recorded as shown in Table V.

Table V

Diluted dispersion applied Time for penetration A> 60 min.

30 b 31 min.

C 5 min.

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Tests on kraft paper

The treatment dispersions used are of the same type as described in the preceding tests on nonwoven materials, but have a different concentration. Paper 5, Claremont unbleached kraft paper weighing approx. 977 g 2 per m, is dipped with the dispersions as indicated to obtain a wet uptake of 138-2%. The paper is then dried by two passes through one to approx. 104 ° C heated filler, once with each side facing up. Contact time is 75 seconds. The treated papers and an untreated control are subjected to the AATCC oil rejection test and the results are given in Table VI.

Table VI

Synthesized _ Processed Paper_ 15 Dispersion Active Ingredient Fluorine Content Oil Rejection D Ex. 3 0.08% 4-5 E 3 0.04% 1-2 F 4 0.08% 5 G 4 0.04% 1-2 20 H 9 0.08% 5 J 9 0.04% 4 ubeh. paper - 0.00% 0

Example 10 Chlorination of triallyl trimellite adduct without solvent Product of Example 1 984 g

Chlorine 117 g Saturated aqueous sodium bisulfite solution 290 ml 30% aqueous sodium hydroxide solution 455 ml 30 The product of Example 1 (984 g) is charged to a 3 liter round bottom flask with a bottom outlet, equipped with a heating sheath and a cooling finger for cooling with aqueous water. Nitrogen is passed through the flask while the contents are heated to 85 ° C for melting. The contents of the flask are shaken while chlorine gas is introduced below the liquid surface as further described below.

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Elapsed time Temperature (min) (° C) Actions and remarks O 82 Cl2 started 30 84 14 g Cl2 added 5 65 83 37 g Cl2 added 90 76 61 g Cl2 added 145 61 117 g Cl2 added. Cl2 stopped and N2 feed started 160 60 250 ml of water added 10 162 52 started addition of

NaOHO₂ solution 162-200 52-79 (fluorinating) 200 68 stopped addition of 15 NaHSOop solution 201 67 started addition of

NaOH solution 220 63 stopped flushing

NaOH solution, pH = 3.7 20

The shaking is stopped and the mixture is allowed to cool to room temperature and left overnight. The following morning, the mixture is heated to 70 ° C and the upper aqueous layer removed with the aid of a swab. 400 ml of water and 490 ml of methyl isobutyl ketone are added and the mixture is heated with stirring from 55 to 68 ° C. Stirring is stopped and the upper aqueous layer is removed with a siphon. Add 400 ml of water (preheated to 75-80 ° C) and stir for 15 minutes at 70-80 ° C. Stirring is stopped and the lower organic layer is drained. It has a weight of 1245 g. A sample is dried in a vacuum oven at 90-100 ° C for 1 hour and exhibits a content of 64.7% volatiles corresponding to 806 g of product, ie. a yield of 95%. NMR (proton) examination of the vacuum dried product confirms that the product of Example 3 has been re-manufactured.

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Example 11

Chlorination of triallyl citrate adduct without solvent Product of Example 2 399.6 g

Chlorine 45 g 5 Saturated aqueous sodium bisulfite solution 210 ml 30% aqueous sodium hydroxide solution 105 ml

A 1 liter round bottom flask with bottom outlet is used. A jacket (Glas-Col) is used for heating. The product of Example 2 is charged to the flask at room temperature and 10 melted under nitrogen. Then, the contents of the flask are stirred while chlorine gas is introduced below the liquid surface in accordance with the following scheme:

Progress to Temperature 15 (min.) (° C) Actions and Remarks 0 83 CI2 started 20 85 11 g Cl2 added 50 83 29 g Cl2 added 78 83 45 g Cl2 added.Cl2 stopped, 20 N2 “addition started 100 83 added 200 ml of H2 O

101 58 reheat to 80-85 ° C

110 81 started addition of

NaHSO 2 solution 25 125 84 completed addition of

NaHSO4 solution 130 83 started adding

NaOH solution 160 completed addition of 30 NaOH solution 170 85 pH = 3.5

Stirring is stopped at this point and the upper aqueous layer is removed with a siphon. 300 ml of water is then added and the mixture is reheated to 88 ° C with stirring. stirring

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29 the ring is stopped and the molten product (330 g) is drained from the bottom. A sample of the product is dried at 100 ° C in a vacuum oven and shows a content of 95% non-volatiles. This represents 91% of the theoretical yield. Elemental analysis gives the following 5 results:

Elemental Calculated,% Found,% C 28.2 31.62

Cl 6.4 6.4 F 58.4 56.6 10 H 1.2 0.98 In 0.0 0.76 NMR (proton) and elemental analysis shows that the product has the structure set forth in Example 4.

15

Example 12

Preparation of MPI / diallyl isophthalate (DAIP) adduct MPI 8655 g DAIP 1980 g 20 ABI 60 g

All MPI is placed in a round bottom flask placed in a water bath for temperature control. 600 ml of DAIP is added and the mixture is deoxygenated. The mixture is heated to 72 - 3 ° C, followed by the following scheme of addition: 25 30 35 0

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Elapsed time ABI addition (g) DAIP addition (ml) O 6 58 200 60 6 5 89 200 118 200 120 6 178 200 180 6 10 238 200 240 6 298 residue 300 6 360 6 15 420 6 28 480 6 540 6 1410 temperature raised to 76 ° (material 20 was partially frozen) 1410-1450 temperature gradually raised to 82 ° to melt product 1485 reaction completed 25 Chlorination of adduct 4000 g of the above described adduct and 2775 g 1.1.2-- Trichloro-1,2,2-trifluoroethane is placed in a round bottom flask with bottom outlet and reflux condenser and heated until the contents can be stirred, ie. to a temperature of approx. 40 ° C.

520 g of chlorine are added under the surface of the liquid over a period of 3.5 hours while maintaining the temperature between 35 and 50 ° C and 1 liter of water is then added. Over a period of 2.5 hours, 2200 ml of a saturated aqueous solution of sodium bisulfite is added at a temperature in the range of 32 to 50 ° C.

35 During cooling to maintain the temperature in the region of

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31 limb 30 and 50 ° C, 30% aqueous sodium hydroxide solution is added. When the pH reaches 5.4 after 1.5 hours, the addition of aqueous sodium hydroxide solution is stopped, using 1865 ml thereof. During the addition of the sodium hydroxide solution, some salts are formed on the inside of the neck of the flask. One liter of water is used to periodically flush the salts from the neck of the flask. The mixture is left for 1/2 hour, then the top aqueous layer is removed. 2900 ml of water, 250 ml of 1,1,2-trichloro-1, 2,2-trifluoromethane and 250 ml of isopropanol are added and the mixture is shaken and then allowed to stand. The product in solution in chlorofluorocarbon (a pale amber solution) is withdrawn at the bottom. The product weighing 534 g contains 57.4% solids (by drying in a vacuum oven at 90-100 ° C), corresponding to 3072 g of product, a yield of 83.6%. The solution is a very pale amber liquid in solution. The NMR spectrum is in accordance with the following structure: 0 CH2 Cl1 J + ° -CH-CH2-CnF2n + 1 20 OJ_c_O_cH-CH2-cnF2n + 1 o CH2 Cl1 25 30 35

Claims (20)

1. Polyfluoroalkyl esters, characterized in that they have the general formula 5 f 0 Ί Rf CH 2 CHOC-R 1 contains at least 3 carbon atoms, is an optionally substituted alkyl, aryl, aralkyl, cycloalkyl or cycloalkenyl group and n is a number from 1 to 4. A compound according to claim 1, characterized in that Rf is a perfluoroalkyl group containing from 3 to 20 carbon atoms, R is an optionally substituted alkyl, aryl, aralkyl or cycloalkyl group and n is a number from 2 to 4 20 A compound according to claim 2, characterized in that R 1 is derived from citric acid, o-, m- or p-phthalic acid, succinic acid, chlorendic acid or a benzene polycarboxylic acid. A compound according to any one of claims 1-3, characterized in that R 1 contains from 4 to 16 carbon atoms. Is a saturated, monovalent, non-aromatic fluorinated aliphatic group which is straight or branched or cyclic, and contains at least 3 carbon atoms, R 1 is an optionally substituted alkyl, aryl, alkenyl, aralkyl, cycloalkyl or cycloalkenyl group, and n is a number from 1 to 4 during said reaction wherein the reactant compound is in molten form or dissolved or suspended in a liquid medium which is inert under the reaction conditions. A compound according to claim 3, characterized in that R 1 has on average from 6 to 8 carbon atoms. 30 Process for the preparation of a polyfluoroalkyl ester according to claim 1, characterized in that chlorine is reacted with a reactant compound of the general formula 35 16 RfCH2CHCH2OC-R1 ΐ Process according to claim 6, characterized in that Rf is a perfluoroalkyl group containing from 3 to 20 r in C atoms, R is optionally substituted alkyl, aryl, aralkyl or cycloalkyl, and n is a number from 2 to 4. Process according to claim 7, characterized in that Rf is a perfluoroalkyl group containing from 3 to r in 20 C atoms, R is derived from citric, o-, m- or p-phthalic acid, succinic acid, chlorendic acid or a benzene polycarboxylic acid, and n is a number from 2 to 4. Process according to any one of claims 6-8, characterized in that Rf contains 4-16 C atoms. DK 162979 B Process according to claim 9, characterized in that it has an average value of 6-8 C atoms. A method of imparting oil or water repellent properties or resistance to dry soiling to a material, particularly carpets, other woven and nonwoven textile materials or paper, characterized in that the material is applied to at least one compound according to claim 1. Process according to claim 11, characterized in that it is a perfluoroalkyl group containing from 3 to r in Is optionally substituted alkyl, aryl, aralkyl or cycloalkyl, and n is a number from 2 to 4. Process according to claim 12, characterized in that R 1 is derived from citric acid, o-, m- or p-phthalic acid, succinic acid, chlorendic acid or a benzene polycarboxylic acid. Process according to any one of claims 11-13, 20 characterized in that R 1 contains 4-16 C atoms. Process according to claim 13, characterized in that R 1 has an average value of 6-8 C atoms. Material, in particular carpets, other woven and nonwoven textile materials or paper exhibiting oil and water repellent properties or resistance to dry soiling, characterized in that it has at least one compound according to claim 1 applied thereto. 30 Material according to claim 16, characterized in that Rf is a perfluoroalkyl group containing from 3 to 20 C atoms, R is an optionally substituted alkyl, aryl, aralkyl or cycloalkyl group and n is a number from 2 to 4 35 DK 162979 BO Material according to claim 17, characterized in that R 1 is derived from citric acid, o-, m or p-phthaisic acid, succinic acid, chlorendic acid or a benzene polycarboxylic acid. 5 Material according to any one of claims 16-18, characterized in that Rf contains from 4 to 16 c atoms. A material according to claim 18, characterized in that R.e has an average value of 6-8 C atoms. 10 1 15 20 25 30