PERFLUOROALKYL SUBSTITUTED POLYMERS

Abstract: Perfluoroalkyl alkylene substituted polydienes are de­ scribed which are obtained by addition of perfluoroalkyl-­ alkylene thiols to polydienes and which are useful as hard, oil- and water repellent coatings on metal, paper, wood, glass, ceramics, textiles or leather.

Description: Perfluoroalkyl substituted polymers The present invention relates to perfluoroalkyl substituted polymers. Polymers containing long perfluoroalkyl groups pendant to the main chain are widely used as oil- and water repellent coatings on textiles and paper. Usually such polymers are prepared by polymerization of a perfluoroalkyl group containing monomers, for instance esters of acrylic, methacrylic or fumaric acid with Rf(CH2)nOH as described in f 2n U.S. 3,068,187, 3,304,278, 4,150,225 or by polycondensation of perfluoroalkylsubstituted diols with diisocyanates, as described in U.S. 3,499,940, 3,720,639, 3,935,277, 4,046,944, and 4,098,742. In each case fluoroalkyl groups containing monomers are the starting material for the corresponding polymer. Due to the bulkiness of the perfluoroalkyl group and its high molecular weight it is difficult and in most structures impossible to reach the high degrees of polymerization necessary to get coatings or shaped articles of great toughness. In addition, the insolubility of highly fluorinated monomers in common organic solvents complicates the synthesis. For these reasons, the perfluoroalkyl substituted polymers reported in the literature are copolymers with non-fluorinated monomers.; in this manner high molecular weight polymers can be prepared, but of a relatively low fluorine content. It has now been found that when perfluoroalkyl substituted thiols are added to a preformed, unsaturated polymer, highly fluorinated prepolymers are obtained which can be used to make tough, abrasive-resistant and oil and water repellent coatings or articles. It is thus one object of the present invention to provide novel perfluoroalkyl-alkylene substituted polymers or copolymers of 1,4butadiene or isoprene with from 40 to 4000 connected carbon atoms in the chain, optionally terminated on one or both ends thereof with a condensation reactive group and containing at least one unit of one of the following structures for every 100 carbon atoms: EMI2.1 wherein X is -S-, -SO- or S02-, R1 is alkylene of from 1 to 16 carbon atoms or is -R1-Q-R3-, wherein R1 and R3 are alkylene groups of 1 to 16 carbon atoms, with the sum of carbon atoms being not greater than 25 and Q is -0-, or -NR4-, wherein R4 is hydrogen or alkyl of 1 to 4 carbon atoms, R2 is hydrogen or methyl and Rf is perfluoroalkyl or perfluoroalkoxyperfluoroalkyl of 4 to 20 carbon atoms. Another object is a process for the manufacture of the inventive perfluoroalkyl-alkylene substituted polymers. Still another object is a process for rendering various substrates oil- and water-repellent. R1 in the structure units (A) and (B) denotes alkylene preferably having I to 16 carbon atoms. Suitable alkylene radicals are thus for example methylene, ethylene, propylene, butylene, hexylene, further octylene, nonylene, decylene, undecylene, dodecylene, tetradecylene and hexadeylene as well as isomers thereof. Preferred are those alkylene radicals R1, which contain 2 to 6 carbon atoms. Ethylene is mostly preferred. Further, R1 denotes a linking group of the formula -R11Q-R3-, wherein R1' and R3 are alkylene of preferably 1 to 16 carbon atoms (for suitable alkylene radicals cf. above). However, it is preferred, that the sum of the carbon atoms in R' and R should not be greater than 25. Q de 1 3 notes a divalent radical such as -0- or -NR4-, wherein R4 is hydrogen or alkyl of 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. Hydrogen and methyl are the preferred radicals R 4 R2 is hydrogen or methyl. Rf denotes perfluoroalkyl or perfluoroalkoxyperfluoroalkyl each having preferably 4 to 20 carbon atoms and may be present as mixtures. These radicals can be represented by the formula F2n+) EMI3.1 wherein n is 4 to 20 if k is 0, and n+m is 4 to 20 if k is 1. n-Perfluoroalkyl radicals, especially those containing 4 to 18 carbon atoms, are preferred, as well as those perfluoroalkoxyperfluoroalkyl radicals having 4 to 13 carbon atoms. The linking group X is a sulphur containing divalent group such as -S-, -SO- or -S02-, where -S- is more preferred. In preferred perfluoroalkyl-alkylene substituted polymers according to the present invention, R1 denotes alkylene of 2 to 6 carbon atoms, R2 is hydrogen or methyl, Rf is a n-perfluoroalkyl of 4 to 18 carbon atoms and X is -S-. In addition to groups (A) and (B), the polymer may also contain up to 40 mole percent of other conventional copolymer groups (C), preferably EMI3.2 wherein R5 is hydrogen or lower alkyl and R6 is hydrogen or lower alkyl, incorporated into the original poly-diene by copolymerization therewith. By "lower alkyl" are meant those alkyl radicals having from 1 to 6 carbon atoms. Other conventional copolymer groups (C) include those copolymer units of conventional monomers, such as methyl, ethyl and C6 to C12 aryl esters of acrylates, methacrylates, maleates, fumarates, and itaconates; vinyl esters having 1 to 18 carbon atoms in the ester group, such as vinyl acetate, butyrate, laurate, stearate and benzoate; vinyl chloroacetate and isopropenyl acetate; C1 to C20 alkyl vinyl ethers, including methyl vinyl ether and n-octadecyl vinyl ether; vinyl halides, including vinyl chloride, vinylidene chloride, vinyl fluoride; methacrylonitrile; chloroprene; halogenated butadienes such as 2fluoro-butadiene, tri- and pentafluorobutadiene; and halogenated styrenes, such as p-chlorostyrene. Furthermore, the polymer may contain up to 20 Z mole of structural units (D): EMI4.1 EMI4.2 wherein R7 is an aliphatic, aromatic or aryl-alkylene group of up to 30 carbon atoms which is unsubstituted or substituted with functional groups including hydroxyl, amino, mono- or di-(lower) alkylamino, carboxy, siloxane or halogen, and X and R2 are as defined above. When present, each of (C) and (D), respectively are present in an amount of at least about 0.01 mole percent. Structures (A) are obtained by addition of perfluoroalkyl-alkylene thiols onto the internal double bonds of polydienes whose monomer units are connected in the 1,4-manner; structures (B) are derived by addition to the external double bonds of polydienes whose monomer units are connected in the 1,2-manner. Polymers containing (A) where X is -S-, can be considered copolymers of perfluoroalkylalkylene-vinyl thioether, polymers with units (B) are copolymers of perfluoroalkyl alkylene -butene-1,2-thioether. Preferably, the novel polymers according to the present invention consist of polymers or copolymers of butadiene and/or isoprene, connected in the 1,4- and/or 1,2 manner (head-tail and head-head) and which may contain units of acrylonitrile or styrene or alpha-methylstyrene or other copolymerizable monomers (C), and which as a molecular weight of 500-500,000, substituted by perfluoroalkyl alkylene group, as in (A) and (B), to such an extent that at least 1 perfluoroalkyl group is present for every 100 connected carbon backbone atoms. The polymer may further be substituted by linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon moieties with from 2 to 30 carbon atoms, which moieties may also contain hydroxy, amino, carboxy, or other functional groups, with up to about 20 of such non-fluorinated groups for every 100 connected backbone carbon atoms as in (D). All pendant substituent groups, fluorinated or non-fluorinated, are advantageously connected to the original poly-diene by either sulfur, sulfoxide or or sulfone linkages. The process for the manufacture of the novel Rf modified polymers comprises reacting a perfluoroalkyl-alkylene thiol Rf-Rl-SH, wherein Rf and R1 are as defined, with polybutadiene or isoprene or a copolymer thereof in a suitable solvent or heat in the presence of a freeradical generating initiator. The corresponding sulfoxides and sulfones are advantageously derived from the thio-ether product by an oxidation step. These polymers are useful as non-wettable, hard coatings for metal, glass, ceramics, masonary, wood, fibers, textiles, plastics or other substrates or they can be fabricated into tough polyurethane rubbers, epoxies or polyesters. The perfluoroalkyl thiols employed in the manufacture of the compounds of this invention are well known in the art. For example, thiols of the formula Rf-Rl-SH have been described in U.S. 2,894,991; 2,961,470; 2,965,677; 3,088,849; 3,172,190; 3,544,663 and 3,655,732. Thus U.S. 3,655,732 discloses mecraptans of formula Rf-Rl-SH, wherein R1 is alkylene of 1 to 16 carbon atoms and Rf is perfluoroalkyl and teaches that halides of formula Rf-Rl-Hal are well known; reaction of RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of RfCH2 I with ethylene gives RfCH (CH CH ) I as is 2 2 2a further taught in U.S. 3,088,849; 3.145,222, 2,965,659 and 2,972,638. U.S. 3,655,732 further discloses compounds of formula R-R1-X-R3-SH, wherein R1 and R3 are alkylene of 1 to 16 carbon atoms, with the sum of the carbon atoms of R1 and R3 being no greater than 25; Rf is perfluoroalkyl of 4 through 14 carbon atoms and X is -S- or -NR4-, where R4 is hydrogen or alkyl of 1 through 4 carbon atoms. U.S. 3,544,663 teaches that the mercaptan of the formula RfCH2CH2SH, wherein Rf is perfluoroalkyl of 5 to 13 carbon atoms, can be prepared by reacting the perfluoroalkyl alkylene iodide with thiourea or by adding H2S to a perfluoroalkyl substituted ethylene (Rf-CH=CH2), which in turn can be prepared by dehydrohalogenation of the Rf-CH2CH2-Hal. The reaction of the iodide Rf-Rl-I with thiourea followed by hydrolysis to obtain the mercaptan Rf-Rl-SH is the preferred synthetic route. The reaction is applicable to both linear and branched chain iodides. Many useful perfluoroalkoxyalkyl iodides are described in U.S. 3,514,487 of the general formula (CF3)2CFO CF2CF2(CH2CH2) I, wherein m is 1 to 3. Particularly preferred herein are the thiols of formula Rf CH2CH2SH, wherein Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can be prepared from RfCH2CH2I and thiourea in very high yield. Preferred perfluoroalkylalkylenethiols are those of the following formulae: C4F9CH2CH2SH, C6F13CH2CH2SH, C8F17CH2CH2SH, C10F21CH2CH2SH, C12F25 CH2CH2SH and EMI7.1 where C6F13CH2CH2SH, C8F17CH2CH2SH and CloF21CH2CH2SH are especially preferred, and mixtyres thereof. Suitable polydienes for the manufacture of the novel polymers are homoor copolymers of butadiene, such as polybutadienes with ratios of 1,4 to 1,2 connected units of 80 : 20 to 10 : 90. These are typical values of what is commonly called 1,4-polybutadiene and 1,2-polybutadiene. Poly-(styrene-co-butadiene), poly(acrylonitrile-co-butadiene) and poly-(alpha-methyl styrene-co-butadiene) are especially preferred copolymers. The polymers can be terminated by functional groups on one or both ends, such as: carboxy-, hydroxy-, mercapto-, amino-, epoxy- and isocyanate groups. The polymers have typically a molecular weight of about 400-10,000, preferably of about 900-6,000. Polybutadienes with terminal condensation reactive groups are especially useful since they can be used in polycondensation reactions, for instance in polyurethane and epoxy formulations. Functional groups may also be attached to the backbone. The reaction is carried out in an ampoule or a flask under nitrogen with good mixing. Initially the reaction mixture is often whitish at room temperature due to the insolubility of RfCH2CH2 SH in the dienepolymer solution. After the reaction is completed (about 3 hours at about 80"C in the case of benzoyl peroxide as initiator) the cooleddown solution is clear, unless the fluorine content is so high that the product is insoluble. Any solvent which will dissolve the polydiene at the reaction temperature can be used. Such solvents are aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, ketones, esters, ethers and alcohols. Useful solvents include heptane, acetone, methyl-ethyl ketone, dimethylformamide, tetrahydrofuran, Nmethy1pyrro1idone, and butyl acetate. Alternately, the reaction can be carried out in bulk, if the viscosity of the polymer at reaction temperature is sufficiently low. The free radical generating initiators can be any of the commonly used peroxy compounds with a suitable half-life time at the reaction temperature, such as benzoyl, peroxide, lauroyl peroxide, or it can be of the azotype, for instance, Azo-bis-isobutyronitrile. The initiators are used at concentrations of from 0.01 % to 1 %, based on weight of reaction. 50 - 70 % of the double bonds in commercial 1,2-polybutadiene (containing 90 Z of 1,2-connected units) can be substituted with RfCH2CH2SH, but only 10 to 20 % of the double bonds in 1,4-polybutadiene (containing 20 Z of 1,2-connected units). Highly fluorinated products can be obtained as clear viscous resins either in solution or in bulk and which have little or no 1,2-double bonds left, according to IR analysis. An Rf-thiol of a molecular weight of about 500 and the polydiene can be reacted in weight ratios from 1:99 to 90:10 in the case of 1,2-polybutadiene, 1:99 to 60:40 in the case of 1,4-polybutadiene. In the case of diene copolymers the upper ratio is correspondingly lower because of the lower concentration of double bonds. Polymers containing up to 70 Z RfCH2CH2SH (about 45 % of fluorine) are soluble in heptane, polymers with higher Rf content need increasing amounts of FREON# or hexafluoroxylene for dissolution. Any unreacted Rf-thiol can be removed by stripping the product in vacuo at elevated temperature. The Rf-substituted polydienes can be used as is, or they can be extended with other suitable polymers and applied to substrates to form coatings with low free surface energy, which are therefore highly oiland water repellent. They can be cured by peroxides or metal salts and heat through the remaining double bonds and they can be reacted with other double bond containing compounds, such as acrylates, methacrylates, styrenes, vinylesters, vinylethers, fumarates, maleates, etc. If they contain terminal reactive groups, they can be used in polycondensation reactions to form, for instance, polyurethanes. It is also possible to carry out more reactions with the remaining double bonds, such as addition of thioglycolic or thiopropionic acids to make a water soluble resin, or of thiols in general (n-alkyl thiols). Other additionreactions which can be carried out are addition of chlorine or bromine, of hydrochloric acid, of vinyl compounds such as acrylate, fumarate, styrene, maleic anhydride. In the following examples (as well as throughout the whole specification) RfCH2CH2 SH denotes a mixture of thiols with the following distribution of Rf chain lengths: C6F13-: 25 % C8F17-: 50 % C10F21-: 25 % 1,4-polybutadiene (poly-BD resin from Sinclair) used in the examples refers to a low molecular weight resin, containing 20 Z 1,4-cis, 60 % 1,4-trans and 20 Z 1,2-connected units. 1,2-polybutadiene ("HYSTL" resin from HYSTL Development Corp.) is a low molecular weight resin containing 10 % 1,4-trans and 90 % 1,2-units. Oxidation of the Rf-thioether substituted polymers to the sulfoxides or sulfones is preferably carried out in solution using any of the conventional oxidizing agents, like organic peroxides such as peroxy acetic acid, hydrogen peroxide, permanganate or chromate. Alternatively, the oxidation can be carried out in the solid dry state by surface oxidation of a coating, for instance with peroxide. The following examples 1 to 15 describe the addition reaction of Rf- alkylene thiols to different poly-butadienes. Example 1: 2 g RfCH2CH2SH, 2g 1,4-polybutadiene (MW:1000), 0.1 g azo-bis-isobutyronitrile (AIBN) and 6.7 g heptane werde sealed in an ampoule under nitrogen and shaken at 6O0C for 3 1/2 hours. After cooling, the reaction product was obtained as a clear solution in 99 % yield as determined by stripping of volatiles in vacuo at 100 C. Example 2: Example 1 was repeated, but with 1,2-polybutadiene (MW:1000). The product was again obtained as a clear solution in 99 X yield. Examples 3 to 5: Using the same procedure as in Example 1, R CH CH SH f22 and 1,4-polybutadiene (1,4-p-Bu) (MW:1000) were reacted in different ratios with the following results: Table 1: EMI11.1 <tb> Example <SEP> No. <SEP> RfCH2CH2SH <SEP> 1,4-p-Bu <SEP> AIBN <SEP> Heptane <SEP> Rf-CH2CH2SH <tb> <SEP> (g) <SEP> (g) <SEP> (g) <SEP> (g) <SEP> Conversion <SEP> (%) <SEP> <tb> <SEP> 3 <SEP> 4 <SEP> 2 <SEP> 0.1 <SEP> 9 <SEP> 79 <tb> <SEP> 4 <SEP> 6 <SEP> 2 <SEP> 0.1 <SEP> 10 <SEP> 63 <tb> <SEP> 5 <SEP> 10 <SEP> 2 <SEP> 0.1 <SEP> 14 <SEP> 55 <tb> Examples 6 to 10: RfCH2CH2 SH was reacted as in Example 1 with different amounts of 1,2-polybutadiene with the following results: Table 2: EMI11.2 <tb> <SEP> RfCH2CH2SH <SEP> 1,4-p-Bu <tb> Example <SEP> No. <SEP> AIBN <SEP> Heptane <SEP> Conversion <SEP> of <tb> MW:1000 <tb> <SEP> RfCH2CH2SH <SEP> (%) <tb> <SEP> (g) <SEP> (g) <SEP> (g) <SEP> (g) <tb> <SEP> 6 <SEP> 4 <SEP> 2 <SEP> 0.1 <SEP> 9 <SEP> 99 <tb> <SEP> 7 <SEP> 6 <SEP> 2 <SEP> 0.1 <SEP> 10 <SEP> 96 <tb> <SEP> 8 <SEP> 10 <SEP> 2 <SEP> 0.1 <SEP> 14 <SEP> 94 <tb> <SEP> 9 <SEP> 10 <SEP> 2 <SEP> 0.1 <SEP> 14 <SEP> 84 <tb> <SEP> 10 <SEP> 15 <SEP> 2 <SEP> 0.2 <SEP> 17 <SEP> 75 <tb> Examples 11 and 12: A butadiene-styrene copolymer (OH-terminated; MW:4000, 25 % styrene) was reacted as in Example 1 with different amounts of RfCH2CH2SH, with the following results: Table 3: EMI11.3 <tb> <SEP> RfCH2CH2SH <SEP> Conversion <SEP> of <tb> <SEP> Example <SEP> No. <SEP> Copolymer <SEP> AIBN <SEP> Beptane <tb> RfCH2CH2SH <SEP> (%) <tb> <SEP> (g) <SEP> (g) <SEP> (g) <SEP> (g) <tb> <SEP> 11 <SEP> 2 <SEP> 2 <SEP> 0.1 <SEP> 6 <SEP> 75 <tb> <SEP> 12 <SEP> 4 <SEP> 2 <SEP> 0.1 <SEP> 8 <SEP> 72 <tb> Examples 13 and 14: The above experiments were repeated, but with a butadiene-acrylonitrile copolymer (OH-terminated; 15 % acrylonitrile; MW: 3800) instead of the styrene copolymer and methyl-ethyl-ketone (MEK) instead of heptane. The results were as follows: Table 4: EMI12.1 <tb> <SEP> RfCH2CH2SH <SEP> Conversion <SEP> of <tb> Example <SEP> No. <SEP> Copolymer <SEP> AIBN <SEP> MEK <SEP> RfCH2CH2SH <SEP> (%) <tb> <SEP> (g) <SEP> (g) <SEP> (g) <SEP> (g) <SEP> f <SEP> <tb> <SEP> 13 <SEP> 2 <SEP> 2 <SEP> 0.1 <SEP> 6 <SEP> 80 <tb> <SEP> 14 <SEP> 4 <SEP> 2 <SEP> 0.1 <SEP> 8 <SEP> 63 <tb> Example 15: 50 g 1,2-polybutadiene (MW: 1000; OH-terminated) and 70 g RfCH2CH2SH were heated in a 3-neck flask equipped with stirrer, thermometer, condenser and nitrogen inlet tube. At 900C the white, creamy mixture developed a slow exotherm reaction, during which the mixture became clear. After 2 hours reaction time 0.2 g AIBN were added and the reaction continued at 800C for 4 more hours. Unreacted thiol was stripped off in vacuo at 90 C using a nitrogen purge for 1/2 hour. The product was a clear, colorless and almost odorless resin of very high viscosity. Yield: 116 g (94 %). The folowing examples describe the synthesis of anionic and cationic water dispensible Rf-alkylene thiol subsituted polybutadiene. Example 16: 50 g 1,2-polyubtadiene (MW: 1000; OH-terminated) and 50 g RfCH2CH2 SH were reacted in 30 MEK with 0.25 g AIBN to form the adduct at 75 C in 4 hours in 98 % yield. To the clear solution 42.6gmercapto- prop ironic acid (HS-CH2CH2CQOH) were added together with 30 g MEK and 0.2 g AIBN and the reaction continued for 3 hours. The reaction product was obtained in 96 % yield as a viscous 68 Z solution in MEK. Most of the double bonds had been consumed as shown by IR-investigations. This resin, after neutralization with triethylamine, formed a clear solution in water. Example 17: Preparation of Polyurethane Coatings 50 g (0.05 mol) 1,2-polybutadiene (MW:1000; OH-terminated) and 50 g (0.1 mol) RfCH2CH2SH were reacted in 30 g dry MEK using 0.25 g AIBN at 75"C for 4 hours. Then 22.2 g (0.1 mol) of isophorone diisocyanate were added together with 0.05 g triethylamine and the mixture was stirred for 2 hours at 500C, after which time the content of isocyanate has fallen to 6.1 %, indicating formation of an isocyanate terminated prepolymer. A film cast from this prepolymer solution was left to cure on the air and formed a hard, glossy film, having a free surface energy of 13 dynes.cm 1. To another sample of the prepolymer solution were added a molar excess of N,N-dimethyl-propane-l,3-diamine. After all -NCO groups had reacted, acetic acid was added, followed by water. A viscous, white-bluish emulsion was formed. A film cast from this emulsion had an oil- but not water- repellent surface and a free surface energy of 12 dynes.cm1. The following examples describe the synthesis of Rf-substituted polyurethanes and epoxies from Rf-alkylene thiol substituted, functionalized polybutadienes. Example 18: 12,5 g 1,2-polybutadiene (MW: 1430, OH-terminated) was reacted in bulk with 70 g RfCH2CH2SH using 0.25 g AIBN as initiator and letting the exotherm rise to 1000 C. A solids determination indicated after 4 additional hours at 700C nearly complete conversion. 3.25 g isophorone diisocyanate were added dissolved in 50 g dry MEK together with 3 drops triethylamine and the mixture was stirred at 60"C for six hours. Another 50 g dry MEK were added and the solution cooled to room temperature. By evaporating the solvent a straw colored rubber could be isolated from this solution, which was extremely tough, although not cross linked. It contained, as determined by elemental analysis, 44 % fluorine. Example 19: In a similar manner a tough and flexible perfluoroalkyl substituted polybutadiene-polyurethane rubber was prepared from 25 g OH-terminated 1,2-polybutadiene (MW:1430), 70 g RfCH2CH2SH and 7.5 g isophorone diisocyanate. Example 20: 51 g of an epoxy group containing polybutadiene (MW: 800; oxirane content 6.9 %) were reacted at 500C in bulk with 55 g RfCH2CH2SH, using three times 0.1 g VAZO-52 (azoinitiator from Du Pont) over five hours. Unconverted RfCH2CH2SH was stripped off in vacuo at 90"C. Conversion was 88 % and the oxirane content of the product 3.22 % (determined by titration). 5 g of this product were mixed with an equimolar amount of the compound of the formula EMI14.1 and 0.05 g dimethyl-benzylamine as accelerator and heated to 1000C for eight hours. A brown, clear, tough disc of an epoxy-polymer was obtained which was not wetted by heptane and had a water pick-up in 30 days of 0.55 %. The following examples show the use of Rf-mOd ified polybutadiene diols in the manufacture of poly-urethane finishes. Example 21: To a 500 ml three neck flask, equipped with stirrer, thermometer, reflux-condenser, nitrogen-inlet tube and heating mantle were added 92.25 g of OH-terminated 1,2-poly-butadiene (MW: 1000) modified with RfCH2CH2 SR in a ratio of one residual double bond per Rf-chain, 1.27 g trimethylhexamethylenediisocyanate, 92.4 g butylacetate, 0.46 dibutyltindilaurate 10 % in butylacetate and 0.12 g triethyl amine 10 % in butyldichloride solution charged and under stirring heated to 800C. After 9 hours most of the diisocyanate was consumed and 3.65 g dimerdiisocyanate, 1.073 g N-methyldiethanolamine and 4.72 g buylacetate were added. All isocyanate was reacted after 90 min. stirring at 80"C. A yellow paste with a solid content of 50 % and a calculated fluorine content of 51.27 in solids was collected. The paste was postemulsified in the following manner: 86 g deionized water, containing 0.5 g acetic acid (100 %) and 3.06 g of methyl-polyoxyethylene (15)-coco ammonium chloride were heated in a 500 ml beaker to 80 C. 57 g of the Rf-modified PU-solution described above were heated to 80 C and poured into the water/emulsifier solution under stirring with a high speed mixer. This pre-emulsion was homogenized with a high pressure homogenizer for 10 minutes and 300 bar pressure. After transforming the emulsion to a 500 ml flask, butylacetate was distilled under vacuum. An off white emulsion was collected with a solid content of 22.0 % and a fluorine content of 10.7 %. A polyester/cotton fabric treated from treatment bath, combining 1.9 Z of the Rf-emulsion described above, 7 % of a glycol-urea-resin and 1 % of a ZnN03-solution (50 %), at a 50 % add-on level, dried and cured for 5 minutes at 1500C showed an oil repellency rating of 6 (according to the AATCC-test method 118-1972) a spray rating of 100 (AATCC-test 22-1978). The following example shows the oxidation of the thio-ethers to the corresponding sulfone and their performance as oil- and water repellent textile treatments. Example 22: 100 g of a 65 Z butylacetate solution of C8F17CH2CH2SHadduct to 1,2-polybutadiene (1000 MW) having a ratio of 1 Rf-mercaptan to 3 unsaturated groups on the polymer backbone, was poured into a solution of 7.15 g polyoxyethylene O)-hexadecyl ammonium-acetate and 60 g H202 (30 %) in 153.6 g deionized water using a high speed mixer. This pre-emulsion was homogenized for 10 minutes on the high-pressure homogenizer (Type "Gaulin") at 300 bar pressure and 60"C. The obtained emulsion had a solid content of 19.76 % and a calculated fluorine content of 8.3 %. The emulsion was applied onto a polyester/cotton poplin at a 50 % solid add-on level with a treatment bath of the following composition: 0.2 % acetic acid, 7 % of a 53 Z solution of glyoxal urea resin, 1 Z of a 50 % Zn(N03)2 solution and 3.6 % of the emulsion maintained above. The fabric was dried and cured for 5 minutes at 150"C. It had an oil repellency of 5 according to the AATCC-test 118-1972 and a spray rating of 100 (AATCC-test 22-1974), whereas the same emulsion, not treated with R202 during the emulsification had an oil repellency of 1 and a spray rating of 70.

Claims: What is claimed is: 1. A perfluoroalkyl-alkylene substituted polymer or copolymers of 1,4butadiene or isoprene with from 40 to 4000 connected carbon atoms in the chain, optionally terminated on one or both ends thereof with a condensation reactive group and containing at least one unit of one of the following structures for every 100 carbon atoms: : EMI17.1 wherein X is -S-, -SO- or -SO2-, R1 is alkylene of from 1 to 16 carbon atoms or is -R1'-Q-R3-, wherein R1' and R3 are alkylene groups of 1 to 16 carbon atoms, with the sum of carbon atoms being not greater than 25 and Q is -O-, or -NR4-, -, wherein R4 is hydrogen or alkyl of 1 to 4 carbon atoms, R2 is hydrogen or methyl and Rf is perfluoroalkyl or perfluoroalkoxyperfluoroalkyl of 4 to 20 carbon atoms, and optionally further containing up to 40 mole percent of the copolymer groups, EMI17.2 or up to 20 mole percent of the copolymer groups EMI17.3 EMI18.1 wherein R5 and R6 are hydrogen or lower alkyl and R7 is an aliphatic, aromatic or aryl-alkylene group of up to 30 carbon atoms which is unsubstituted or substituted by hydroxyl, amino, mono- or di-(lower) alkylamino, carboxy, siloxane or halogen, and X and R2 are as defined. 2. A polymer or copolymer according to claim 1, wherein X is -S-; R1 is alkylene of 2 to 6 carbon atoms; R2 is hydrogen or methyl; and R is n-perfluoroalkyl of 4 to 18 carbon atoms. f 3. A polymer or copolymer according to claim 2, wherein R1 is ethylene and Rf is n-perfluoroalkyl of 4 to 12 carbon atoms. 4. A copolymer according to claim 1, containing about 0.01 to 40 mole percent of said copolymer groups (C) incorporated into the original poly-diene by copolymerization therewith. 5. A polymer or copolymer according to claim 1, wherein said condensation reactive groups are carboxy, hydroxy, mercapto, amino, epoxy or isocyanate groups. 6. A polymer or copolymer according to claim 5, which is terminated with said condensation reactive groups at both ends thereof. 7. A polymer or copolymer according to claim 6, wherein the terminal condensation reactive groups are hydroxy. 8. A copolymer according to claim 1, wherein (D) is present in an amount of between 0.01 and 20 mole percent. 9. A process for the manufacture of a polymer or copolymer according to claim 1, which comprises reacting a perfluoroalkylalkylene thiol of the formula Rf-Rl-SH, wherein R and R1 are as defined in claim 1 fl f 1 with a polymer or copolymer of 1,4-butadiene or isoprene in a suitable solvent or heat in the presence of a free-radical generating initiator, optionally followed by oxidation of the sulfur linking atom to a sulfoxide or sulfone radical. 10. The polymers or copolymers obtainable by the process according to claim 9. 11. A process for rendering non-wettable metal, glass, ceramics, masonary, wood, fibres and plastics, which comprises applying to said substrates a coating of the polymers or copolymers according to claim 1. 12. Use for rendering non-wettable metal, glass, ceramics, masonary, wood, fibres and plastics of the polymers or copolymers according to claim 1.

Inventors: MUELLER, KARL FRIEDRICH
Applicants: CIBA-GEIGY AG
Application year: 1983
Main classification: C08C19
IPC codes: C09D175, C08G18, C09D5, C08F8, C08C19