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US3546187A - Oil- and water-repellent polymeric compositions - Google Patents
Oil- and water-repellent polymeric compositions Download PDF
US3546187A
US3546187A US3546187DA US3546187A US 3546187 A US3546187 A US 3546187A US 3546187D A US3546187D A US 3546187DA US 3546187 A US3546187 A US 3546187A
Thomas K Tandy Jr
United States Patent Ofiice 3,546,187 Patented Dec. 8, 1970 3,546,187 OIL- AND WATER-REPELLENT POLYMERIC COMPOSITIONS Thomas K. Tandy, Jr.., Newark, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Mar. 10, 1969, Ser. No. 805,814 Int. Cl. C08f 15/26 U.S. Cl. 26080.76 22 Claims ABSTRACT OF THE DISCLOSURE An oiland water-repellent polymer consisting essentially of:
(a) from 75% to 98% by weight of units derived from monomers of structure R CH CH O CCH=CH wherein R is a perfluoroalkyl group of from four to fourteen carbons;
(b) from 25% to 2% by weight of units derived from monomers selected from the class consisting of (1) ROCH=CH wherein R is selected from X(CF ),,CH X being F or H and n one or two, and (CF CH, and
(2) R'OCF=CF wherein R is selected from R, as defined above, and F(CF m being from one to three; and
(c) from to by weight of units derived from monomers selected from the class consisting of (1) CH CR CONHR OH,
(2) CH CR CO R OH, and
(3) CH CR CO R wherein R is H or CH R is an alkylene group of from one to about four carbons, R is an alkylene group of from two to about four carbons and R is epoxyalkyl of at least three carbons; or
(4) mixtures of the above;
and wherein the total percent by weight of units present in the copolymer is 100%.
Preferably the polymers have an inherent viscosity as 0.5% solutions in trichlorotrifluoroethane at 30 C. not in excess of 0.8, and most preferably in the range of 0.1 to 0.35.
BACKGROUND OF THE INVENTION This invention is concerned with new fluorinated oil and water repellents for textiles. More specifically, the invention is directed to such polymers containing and trifluoroethyl vinyl ether.
A wide variety of fluorine-containing polymeric materials are known to be useful for treating textiles to render the textiles oil and water repellent. Such fluorinated polymers usually have their fluorine in the form of pendent perfiuoroalkyl groups as fluorine attached to the polymer backbone does not, in general, greatly contribute to oil and water repellency. While oil and water repellency of a good degree can be obtained and can be made durable to laundering and dry-cleaning, the known oiland waterrepellent fluorinated polymers are deficient in several respects. Some of these deficiencies have limited commercial acceptance of textiles treated with fluorinated oil and water repellents.
The deficiencies are discussed in the immediate paragraphs below.
First, most if not all of these fluorinated polymertreated textiles lose their oil and water repellency after laundering when the textile is dried in air at ambient temperatures. The repellency can in large part be restored by heating as, for example, during pressing or during drying in a heated drier. This lack of repellency after the socalled home wash-air dry laundering has greatly affected usefulness of the fluorinated oil and water repellents in the permanent press garment market, for example, where the entire purpose of the permanent press treatment is to obviate the necessity for pressing or heated drying. A second facet of this problem is, of course, that the laundered fabrics lack any protection provided by oil repellency in particular between laundering and the pressing or heated drying which otherwise restores repellency. The polymers of this invention continue to impart oil and water repellency to textiles after laundering and air drymg.
Second, all of the presently known fluorinated oiland water-repellent polymer systems require a rather high temperature cure after application to develop repellency. The permanent press resins used in textiles also require rather high temperature cures but such cure cannot be applied until after the textile is converted into the final form of the garment and the desired creases applied. Thus, textiles treated with permanent press resins and presently available oil and Water repellents cannot be cured until the garment is complete and therefore do not have any oiland water-repelling properties until the garment is complete. Consequently, a large amount of such textile is soiled by oils and greases during garment manufacture without any benefit being gained from the oil and water repellent. Textile and garment manufacturers would like their permanent press treated fabric to be oil and water repellent during garment manufacture. The polymers of this invention allow fabrics treated with such polymers to be cured at a low temperature without curing any crease-resistant resin present.
A third deficiency of fabrics treated with present oiland water-repellent polymers is that of oily-soiling retention. Oil repellent fabrics, of course, tend to repel oily stains but it is impossible to make them completely resistant to oily stains under all conceivable conditions. For example, oily stain will be forced into a fabric if sufiicient pressure is applied even though the fabric will repel the oily stain when no pressure is applied. During cutting and sewing operations, for example, fabrics can come into contact with oily materials under pressure. Such soiled fabrics containing an oil and water repellent are more difficult to clean because the fabric tends to repel the cleaning medium also (detergent containing water). Such fabrics are said to lack oily soil Washability. The polymers of this invention have better oily soil washability than presently used polymers.
A fourth deficiency of present oil and water repellents is that they have poor ability to resist abrasion. Most fabrics undergo a good deal of abrasive action during their lifetime. Rubbing during flexure or laundering, Sliding of two fabrics together, for example on upholstery, and a variety of other mechanisms all tend to abrade the surfaces of fibers in a fabric. Most, if not all, of the presently known fluorinated oil and water repellents are not particularly resistant to abrasion. Most fabrics, therefore, sooner or later lose their coating of oil and water repellent, especially at points of greatest wear and hence lose their repellency to soiling by oilor water-based materials at these same points. The polymers of this invention resist such abrasive action more than present oiland water-repellent polymers.
Additional deficiencies of present oil and water repellents include lack of durability of the repellent upon laundering or dry cleaning and lack of repellency toward dry-soiling, i.e., toward particulate matter. The polymers of this invention possess good durability and repellency toward dry-soiling.
3 SUMMARY OF THE INVENTION An oiland water-repellent polymer consisting essentially of:
(a) from 75% to 98% by weight of units derived from monomers of structure R,CH CH O CCH=CH wherein R is a perfluoroalkyl group of from four to fourteen carbons;
(b) from 25% to 2% by weight of units derived from monomers selected from the class consisting of (1) ROCH=CH wherein R is selected from X(CF ),,CH X being F or H and n one or two, and (CF CH-, and
(2) ROCF=CF wherein R is selected from R, as defined above, and F(CF m being from one to three; and
(2) CHFOR CO R OH, and
(3) CHFCR CO R wherein R is H or CH R is an alkylene group of from one to about four carbons, R is an alkylene group of from two to about four carbons and R is epoxyalkyl of at least three carbons; or
and wherein the total percent by weight of units present in the copolymer is 100% Preferably the polymers have an inherent viscosity as 0.5% solutions in trichlorotrifluoroethane at 30 C. not in excess of 0.8, and most preferably in the range of 0.1 to 0.35.
DESCRIPTION OF THE INVENTION The polymers of this invention contain two essential ingredients. The first is a monomer of structure wherein Rf is a perfluoroalkyl group of from four to fourteen carbons. From 75 to 98% by weight of such monomer must be present in the polymer. The second essential monomer is chosen from ROCH CH where 'R is X(CF CH X being H or F and n being one or two or (CF CH, and ROCF CF R is R, that is X(CF ),,CH or (CF CH or F(CF 111 being from one to three. From 2 to 25% by weight of this monomer is used.
In the monomers RfCHZCHZOZCCHiHz, the perfiuoroalkyl group R is preferably a straight chain group F(CF where s is from 4 to 14, but may also be branched perfluoroalkyl such as (CF CF(CF where s' is from one to 11. In the preferred form of this invention, R is a mixture of per-fluoroalkyl groups F,(CF where s is predominantly 6, 8 and 10.
The monomers R CH CH O CCH=CH are prepared by esterifying the alcohols R CH CH OH by one of several means, for example, reaction with acrylyl chloride in the presence of a tertiary amine, reaction with acrylic acid in the presence of either an acid catalyst such as sulfuric or toluenesulfonic acids or a tetraalkyl titanate (Werber, U.S. Pat. 3,056,818), or by transesterification of the alcohols R CH CH OH with an alkyl acrylate such as the methyl or ethyl esters in the presence of an acid or a tetraalkyl titanate (Haslam, U.S. Pat. 2,822,- 348). The alcohols R CH CH OH are known compounds, see for example Day, U.S. Pat. 3,283,012.
The monomers R,CH CH O CCH=CH may also be prepared by reaction of the iodides R CH CH I with an alkali metal salt of acrylic acid, using the procedure of Fasick, U.S. Pat. 3,239,557.
It is essential in this invention that the acrylic acid ester monomers R 'CH CH O CCH=CH be used. The corresponding methacrylic acid esters 4 do not result in polymers giving the desired results. The acrylic acid esters must also have the two methylene groups between R; and the ester carbonyl group. For when either of the known groups of acrylic acid esters R,CH O CCH=CH (U.S. Pat. 2,642,416) or 7:3 or more (U.S. Pat. 3,102,103) is substituted for the monomers R 'CH- CH O CCH CH the desired results are again not obtained.
The other essential monomer in the present polymers is the 'vinyl ethers -ROCH=CH or ROCF=CF The monomers ROCH CH may be any one of X(CF CH OCH=CH X=F or H, n=1 or 2, or (CF CHOCH=CH This group of monomers includes HCF CH OCH=CH HCF CF CH OCH=CH and ('CF 'CHOCH=CH Of this group, the preferred monomers are CF 'CH OCH=CH and particularly the former.
These vinyl ethers are prepared from the corresponding alcohols CF CH OH, CF CF CH OH,
m=13 This group of monomers includes Most of these monomers are also known. Those containing the methylene group -CH adjacent to oxygen are prepared by reaction of the sodium salt of the alcohols X(CF CH OH or (CF CHOH with tetrafluoroethylene, as taught by Dixon in U.S. Pat. 2,917,548. The monomers F(CF OCF=CF are prepared by a different route. The most convenient method is that taught by Harris and McCane in U.S. Pat. 3,132,123, namely reaction of an acid fluoride F(CF COF with cesium fluoride and hexafiuoropropylene oxide to form hydrolysis to the acid F(CF OCF(CF )CO H followed by pyrolysis of the acid to the olefin F (CF OCF=CF Other references teaching reaction of acid fluorides F(CF COF with hexafluoropropylene oxide are Moore et al., U.S. Pat. 3,250,808 and Moore, French Pat. 1,362,548. Other disclosures of conversion of the acids or acid fluorides to olefines are contained in Fritz et al., U.S. Pat. 3,114,778; Fritz et al., U.S. Pat. 3,291,843, Lorenz, U.S. Pat. 3,321,- 532; Harris and McCane, U.S. Pat. 3,180,895.
It is essential in the present invention that at least 2% by weight of the monomers ROCH CH or R'OCF=CF and no more than 25% of such monomers be present. If less than 2% or more than 25 of such monomers are present, the desirable properties of the polymers are no longer obtained. The preferred concentration of these monomers is in the range of 3 to 10%.
Although it has not been found to be essential, it is often desirable to include in the polymers of this invention small amounts of certain monomers which can lead to greater durability to dry-cleaning and laundering. These monomers are preferably N-hydroxyalkyl acrylamides of structure CHFCR CONHR OH, hydroxyalkyl acrylic esters of structure CH CR CO R OH or epoxyalkyl acrylic esters of structure CH CR CO R where, in all cases, R is H or CH R in the amides is hydroxyalkyl of one to about four carbons, R in the esters is hydroxyalkyl of two to about four carbons and R is an epoxyalkyl group of three or four carbons. Some of these monomers are commercially available, e.g. N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethy1 acrylate, 2- hydroxyethyl methacrylate, glycidyl acrylate and glycidyl methacrylate. The other hydroxyalkylamides are readily available by reaction of acryloyl or methacryloyl chloride with hydroxyalkylamines such as ethanolamine, 2-hydroxypropylamine, 3-hydroxypropylamine, Z-hydroxybutylamine, 3-hydroxybutylamine or 4-hydroxybutylamine. Other hydroxyalkyl acrylates or methacrylates are available by esterification of one mole of acrylic or methacrylic acid with one mole of diols such as 1,2-propylene diol, 1,3-propylene diol, 1,2-butylene diol, 1,3- butylenediol or 1,4-butylene diol. Other epoxyalkyl esters are available from the epoxy butanols.
Of these monomers, the commercially available monomers are preferred, i.e. N-methylol acrylamide or methacrylamide, 2-hydroxyethyl acrylate or methacrylate or glycidyl acrylate or methacrylate.
Mixtures of two or more of these monomers may be used and, in some cases, such mixtures are preferred, for example equal weights of N-methylol acrylamide and 2- hydroxyethyl methacrylate.
It is necessary to use 0.1% by weight of such monomers to obtain any noticeable effect. There is no benefit in using more than 5% and larger amounts have undesirable effects on the polymer properties. About 0.5 of such monomers is preferred.
As noted earlier, these monomers are optional in the polymers of this invention. Perfectly satisfactory durability exists to laundering when they are completely absent although a better, more durable product may be available when they are present.
No significant amounts of monomers other than the aforementioned types should be present in the polymers of this invention, as indicated earlier, or the desirable properties will belost.
Although the polymers of this invention may be prepared by solution polymerization techniques Well known in the art, it is preferred to use aqueous emulsion techniques. In the broadest sense, any known free radical initiator may be used, including both water soluble and water insoluble types. Among the water soluble types are inorganic peroxides such as sodium peroxide, barium peroxide or ammonium or potassium persulfate and water soluble azo compounds such as azobis(isobutyramidine) dihydrochloride. Among the water insoluble types are peroxy anhydrides such as benzoyl peroxide, peroxy esters such as tert-butyl peroxy pivalate, tert-butyl peroxy benzoate, hydroperoxides such as tert-butyl hydroperoxide, ditertiary alkyl peroxides such as ditert-butyl peroxide, or water insoluble azo compounds such as azobis (isobutyronitrile), azobis(dimethylvaleronitrile) and the like. Redox initiators such as the combination of ammonium persulfate, sodium bisulfite and ferrous sulfate are also useful.
In general, the Water soluble initiator azobis(isobutyramidine)dihydrochloride is the initiator of choice.
The polymerization temperature is, quite naturally, chosen to suit the initiator being used. Those skilled in 6 the art are well aware of the temperatures appropriate to each of the aforementioned initiator types.
The polymerization is carried out by first emulsifying the monomers in water, then bringing the reaction mass to the desired temperature and adding the initiator. It may be desirable, albeit not essential, to homogenize the monomer-water mixture before heating. As many of the monomers ROCH CH and ROCF=CF as earlier defined are relatively low boiling compounds, often lower boiling than the desired polymerization temperature, provision should be made to retain these monomers in the reaction system. This is readily accomplished by use of either an efiicient reflux condenser on the reaction vessel or by using a sealed autoclave for the polymerization.
Emulsifying agents must, of course, be used to obtain aqueous emulsions. Either cationic or anionic types are more preferred than the nonionic types. Mixtures of nonionics with either other type may be used. Useful cationic types are the well-known quaternary ammonium salts of long chain fatty amines,
where R is an alkyl group of at least twelve carbons. In general, R is a lower alkyl group such as methyl and X- is an inert anion such as chloride ion. A typical group of such agents are the ammonium salts sold by the Armour Co. under the trade name Arquad. These are n-alkyl trimethyl ammonium chlorides where the alkyl has from 12 to 18, preferably 16, carbons. These are the preferred cationic dispersing agents. Another type of cationic agents is the acetate salts of n-alkyl dimethylamines Where alkyl again contains 12 to 18 carbons. These salts are perfectly suitable insofar as the polymerizations are concerned but have a slight deleterious effect on oily-soil washability of the product polymers on fabric, hence are not preferred.
Useful anionic emulsifying agents include both the alkali metal salts of alkanesulfonic acids and alkali metal salts of monoalkylsulfuric acid esters, where alkyl again is from 12 to 18 carbons. Fatty acid soaps may be used, provided the fatty acid is relatively free of unsaturated acids.
It is generally preferable, if the most advantageous polymer properties are to be obtained, that the inherent viscosities of the polymers of this invention be below 0.8, when measured at 30 C. as 0.5% solutions in trichlorotrifluoroethane. Inherent viscosity is determined by the formula 1 V VZ '6 ln where Vi is the inherent viscosity, C is the polymer concentration in grams per ml. of solution, V is the viscosity of the solution, V0 is the viscosity of the solvent and In is the natural logarithm.
In general, very little has to be done to keep inherent viscosity below 0.8 due to the nature of the reacting monomers, vinylethers being rather more eflicient chain transfer monomers than acrylic esters. If necessary, small amounts of chain transfer agents such as dodecyl mercaptan may be added to control molecular weight, hence inherent viscosity.
For use in oil and water repellent formulation, the polymer emulsions obtained by the above procedures are usually used directly in the pad bath without isolation of the polymer.
The compositions are applied preferably as an aqueous dispersion by brushing, dipping, spraying, padding, rollcoating or by any combination of these methods. For example, the prepared concentrated dispersion of polymer composition may be used as a pad bath by diluting it with water to a solids content of 0.1% to 10% by weight of the bath. The textile material is padded in this bath, and is then freed of excess liquid, usually by squeeze rolls, so that the dry pickup (weight of dry polymer on fiber) is between 0.1% and 10% by weight of the fiber. The treated material is then dried by heating, say in an 7 oven at 135 to 172 C. until dry. The dry fabric is oil and water repellent without further heating but such further heating may increase the degree of repellency somewhat. The textile material will retain repellency even after many launderings or dry-cleanings.
It is common practice to treat fabrics with several agents at the same time. These agents may include softeners, crease resistance agents, wetting agents, antistatic agents, resin finishes, soil release agents, flame retardants and the like. When used in the presence of such agents, lower concentrations of the polymers of this invention may be required to obtain equivalent repellency than when used alone. It is also common practice to add auxiliary water repellents to treating baths. In general, far more of the polymers of this invention are required to obtain maximum water repellency than maximum oil repellency. Commercially, it is cheaper to add only as much polymer as is required to obtain the desired oil repellency, than to add the far cheaper water repellents to bring up water repellency to the desired level.
More recently, another development has occurred in the textile trade, the permanent press treatment, as taught, for example, in US. Pat. 2,974,432. In this treatment, a permanent press resin such as described in US. Pat. 3,049,446 is coapplied along with the polymers of this invention. In some cases such resins are not cured, however, until the textile is fabricated into the finished article. It is important, therefore, that the textile is repellent, without anything more than drying, which occurs when using the polymers of this invention, as above indicated.
Suitable substrates for application of the polymers of this invention are fibers, yarns, fabrics and articles made of filaments, fibers or yarns derived from natural, modified natural or synthetic polymeric materials or from blends of these. Examples are cotton, silk, regenerated cellulose, nylon and like synthetic polyamides, fiber-forming linear polyesters, fiber-forming polyacrylonitrile and modified acrylonitrile polymers, cellulose nitrate, cellulose acetate, fiberglass, paper, leather and the like. These may be in many forms of knit and woven fabrics, including sateen, poplin, broadcloth, jean cloth gabardine, upholstery materials, as well as non-woven fabrics and the like used to fabricate rainwear, work clothing, suiting, female clothing, tenting, autobody tops, furniture upholstery, draperies and a variety of others.
The polymers of this invention overcome essentially all of the objections to earlier fluorinated oil and water repellents.
EXAMPLE I Preparation of copolym-ers of this invention (a) A dispersion of 144 parts F CH CH O CCH CH 16 parts of a 50% aqueous solution of octadecyltrimethyl ammonium chloride and 80 parts water was prepared, then diluted with 48 parts further water. The dispersion was purged with nitrogen for 30 min., then 0.095 part 2-hydroxyethyl methacrylate and 0.145 part 60% aqueous N-methylolacrylamide were added and purged for an additional 30 min. Then 16 parts trifluoroethyl vinyl ether were added and the resulting mixture was added to 300 parts further water. While maintaining the mass under a slight positive nitrogen pressure and under an efiicient reflux condenser, the temperature of the mass was raised to 65 C. and 0.32 part azobis (isobutyramidine)dihydrochloride was added. Further like additions of azo compound were made after 20 and 60 minutes, after which the mass was maintained at 65-70" C. for eight hours.
The resulting polymer latex contained 25.52 parts polymer per 100 parts latex, corresponding to a 96.4% monomer conversion. A sample of dried polymer had an inherent viscosity of 0.70 as a 0.5% solution in trichlorotrifluoroethane at 30 C. Nuclear magnetic resonance spectrographic analysis of a hexafluorobenzene solution of the polymer indicated it contained 2.75% by Weight trifiuoroethyl vinyl ether.
The composition of the polymer comprised units of the monomers shown as follows in the weight percents shown:
Percent 'CF CH OCH CH 2.75 CH CHCONHCH OH 0.25 CH =C (CH CO CH CH OH 0.25
(b) The polymerization procedure of part (a) was repeated except that the fluorinated acrylate of part (a) was replaced with F(CF CH CH O CCH=CH and the 2-hydroxyethyl methacrylate and aqueous N-methylolacrylamide were omitted. The resulting polymer contained about 96% by weight of units derived from the fluorinated acrylate and about 4% by weight of units derived from the CF CH OCH CH The inherent viscosity was 0.68.
(c) The polymerization procedure of part (a) was repeated except that the fluorinated acrylate of part (a) was replaced with F (CF CH Cl-l O CCH=CH (wherein n represents the numerals 6, 8, 10, 12 and 14 in the approximate weight ratio 35/30/18/8/3). The resulting polymer contained about 6% by weight of units derived from the fluorinated acrylate, about 4-5% by weight of units derived from the tained about 97.5% by weight of units derived from the fluorinated acrylate, about 2% by weight of units derived from the CF CH OCH=CH and about 0.25% each of the hydroxyethyl methacrylate and methylolacrylamide.
(e) The polymerization procedure of part (a) was repeated except that the fluorinated acrylate of part (a) was replaced with F(CF CH CH O CH CI-I '[wherein n is defined as in part (c)] in an amount of about 131.2 parts; and the amount of the trifluoroethyl vinyl ether employed was 28.8 parts. The resulting polymer contained about 92% by weight of units derived from the fluorinated acrylate, about 8% by weight of units derived from CF CH OCH=CH and about 0.25% each of the hydroxyethyl methacrylate and methylolacrylamide.
(f) The polymerization procedure of part (a) was repeated except that the fluorinated acrylate of part (a) was replaced with F(CF ,CH CH O CCH=CH [wherein n is defined as in part (c)]; and the 2-hydroxyethyl methacrylate and aqueous N-methylolacrylamide Were omitted. The resulting polymer contained about 96% by weight of units derived from the fluorinated acrylate and about 4% by weight of units derived from CF CH OCH=CH The polymer had an inherent viscosity of 0.22.
EXAMPLE II Employing the parts and procedure of Example 1(a), except as indicated, the following polymers were prepared. These polymers are not ones which fall within the scope of this invention and were prepared in order to carry out the comparison tests found in the subsequent examples:
(a) A copolymer of about 94-5% by weight of units 9 derived from F(CF CH O CCH=CH about 6% by weight of units of CF CI-I O--CH=CH and about 0.25% each by weight of units derived from Z-hydroxyethyl methacrylate and N-methylolacrylamide, having an inherent viscosity of 0.80 was prepared by polymerizing the above monomers as described in Example 1(a).
(b) 156.8 parts of F(CF CH 'CH O CCH=CH [wherein n is defined as in part (c) of Example I], 3.2 parts of CF CH OCH=CH and the same amounts of 2-hydroxyethyl methacrylate and N-methylolacrylamide as shown in Example I(a) were polymerized as described in Example 1(a). The resulting polymer contained only about 1% by weight of units derived from (c) A copolymer of F(CF ),,CH 'CH O CCH=CH [wherein n is defined as in Example I(c)] in about 99.5% by Weight units and about 0.25 by weight each of units derived from 2-hydroxyethyl methacrylate and N-methylolacrylamide was prepared by reacting the monomers as described in Example I( a). However, the trifiuoroethyl vinyl ether was omitted. The resulting copolymer had an inherent viscosity of 0.47.
EXAMPLE III The water repellency of the polymer of Example I(c) was compared with that of the polymer of Example II(c) by preparing pad baths with formulations containing each. Each formulation was padded onto a 65/35 polyethylene terephthalate/cotton-Thermosol-dyed poplin fabric until a desired percent wet pick-up on weight of fabric (OWF) of the polymer and other dispersants of the formulation was obtained on the fabric. The desired amount of pick-up is obtained by adjustment of the squeeze rolls. The treated fabrics were then air-dried and cured at about 350 F. for minutes. They were then tested for their initial oil and water repellency and were retested after subjecting them to various home washtumble dry or air-dry or dry-cleaning procedures as described below.
The formulations employed and the percent on weight fabric pick-up are shown in the following table. Four formulations were used labeled A, B, C, and D, i.e., Formulations A and B contained the polymer of Example I(c) and were identical except that the amount of the polymer in Formulation A was sufficient to produce a 2% OWF pick-up on the fabric, while the amount of the polymer in Formulation B was sutficient to produce a 3% OWF pick-up on the fabric. Formulations C and D contained the polymer of Example II(c) and were identical except for the amounts of polymer in each.
Amount of formulation component on fabric (percent OWF) Component of formulation A B C D A 6.54% active ingredient dispersion of the polymer of Example 2 3 C m nN Table I below shows the oil and water repellencies of the fabrics treated with Formulations A, B, C and D initially, after one home wash-air dry, after one home washtuble dry, after five home wash-tumble dry cycles, after one dry cleaning, and after five dry cleanings.
The oil repellencies were determined using Test Method No. 118-1966T of the American Association of Textile Chemists and Colorists, modified in that the oils used contained dissolved therein a blue oil-soluble dye and the determinations were made after three minutes, rather than the 30 sec. required by the aforementioned test. Oilrepellency figures run from 1-6; 6 being good repellency, 1 being poor. Water repellencies were determined by Test Method No. 221952 of the aforementioned association. Water-repellency figures run from 0 to 100 being good repellency, 0 being poor.
Home laundering tests were carried out in a Kenmore washer Model 600 loaded with a 4-lb. load, with 29 g. of Tide. The wash is set at hot (12 min. cycle) and a warm rinse (12 min.). The total washing and rinsing time is 40 minutes. In the home laundering air-dry test, the spundry fabrics are dried at ambient temperatures. In the home laundering tumble-dry test, the spun-dry fabrics are dried at 156-l60 F. in a home drier with tumbling.
The dry-cleaning test consists of agitating the sample for 120 minutes in tetrachloroethylene containing 1.5% (weight/volume) of a commercial dry-cleaning detergent (R. R. Street Co., 886 Detergent), extraction with tetrachloroethylene, drying for three minutes at 66 C. in a drum and followed by a 15-second pressing at 149 C. on each side of the fabric.
The oil and water repellencies of the fabrics before and after the above-described tests are shown in the following Table I:
1 Example To polymer, 2% OWF. 2 Example To polymer, 3% OWF. 3 Example IIc polymer, 2% OWF. 4 Example He polymer, 3% OWF. 6 Home wash air dry.
6 Home wash tumble dry.
7 Dry-cleaning.
These formulations contained no added water repellent, as is usually the case in most oil/water-repellent formulations for commercial textile treatment. Hence water repellency is not as good as would be expected in a full commercial formulation.
EXAMPLE IV Aqueous emulsions of the polymers obtained in Examples I(c), I(d), I(e) and II(b) were prepared in which the emulsion contained 5.4% by Weight of F(CF CH CH O CCH=CH in polymerized form.
Formulations containing the emulsions (or dispersions) meme obtained in the preceding paragraph were prepared as E Q described in Example III using the same ingredients N (other than the polymers). However, the formulations g i were made up such that the percent pick-up on weight of g 511 Q fabric of the polymers was 1, 2 and 4%, while the per- '56 Z a cent pick-up OWF for the other components of the formua. E, g E lation was in each, 12% OWF for the crease-proof resin, F i:
2.4% OWF for the catalyst, and 0.05% OWF for the 513 g Q stabilizer. g; g a
The formulations prepared above were tested for their 20 5 oil repellency before and after laundering and cleaning a. tests carried out acocrding to the description in Example E, z wh III. The results of such tests are shown in Table II. E
EXAMPLE v Q3 An emulsion (labeled the First Emulsion in Table III O whim below) was prepared containing 6.48% active ingredient e of the polymer of Example I(c) and containing 7.8% acg l tive ingredient of a copolymer of 2-ethylhexyl methacrylj: ate and N-methylolacrylamide (in which the amount of 33 Q N-methylolacrylamide in the copolymer was about 0.5% fig g by weight). 55 E m A similar emulsion (labeled the Second Emulsion in g; g H Table III below) was prepared which contained only g; g Q 6.48% active ingredient of the. polymer of Example I(c). 55 0 2 Three different formulations were prepared from each a? E of the two emulsions (resulting in 6 formulations in all). 5.5.
One of each set of three was prepared to result in a E g5; percent pick-up on Weight of fabric of the polymer or E polymers in the formulation of 2%. Another of each set Q {5 2 of three was prepared to result in a percent pick-up on H 3 weight of fabric of the polymer or polymers in the formu- 0 lation of 3%. The last of each set of three was prepared a to result in a percent pick-up on weight of fabric of E the polymer or polymers in the formulation of 4%. Each g g of the six formulations contained a water repellent (a i E 3 Q NHHO 25% solids dispersion in water in which the solids were E e 3 47.5% tris(methoxy methyl) tris(behenoyloxymethyl) f .E a g E melamine, 47.5% parafiin wax, and 5% dimethyl fatty 40 a HF amine acetates) in an amount sufficient to result in an fio g E; No on-weight fabric pickup of about 2%; a wash/Wear resin E of triazine-formaldehyde condensate (Aerotex 23 Spe- E g .4
cial) in an amount sufficient to result in an on-Weight 2 71 NNMH fabric pick-up of about 5%; and the catalyst and stabilizer E 2 g used in the formulations described in Example III in amounts sufi'icient to result in an on-weight fabric pick- #1 5g up of about 1% and 0.04%, respectively.
Each of the six formulations was applied to the fabric 5 E i i used in Example III and the fabrics then dried at 340 E E E F., then cured for two minutes at the same temperature. l i E The fabrics were tested for the initial oil and water 5 l i i repellency, for their repellency after 1 dry-cleaning, and u for their repellency after 1 standard laundering (which consisted of agitating the treated fabric for 40 min. at Qfifl C. to 100 C. in Water containing 0.1% by weight 588g neutral chip soap+0.05% soda ash, rinsing with 60 C. 55m water three times, spin drying, then pressing on each face at 300 Eizo" F. for 30 sec.) some The results are shown in Table III. 60 o fg Three formulations were prepared. Each contained a sufficient sodium acetate to provide a 4% pick-up on G5 L 0 weight of fabric of the acetate, suflicient acetic acid to E 5 provide a 0.3% pick-up on weight of fabric of the acid, 3 and sufficient long chain alkyl pyridinium chloride water E 51 225 repellent to provide a 4% pick-up on weight of fabric :5 of the chloride. In addition, one formulation contained S sufficient 6.5% active ingredient emulsion of the polymer 8 of Example I(c) to provide a 2% pick-up on weight of QEEIE fabric of the polymer. The second formulation contained i a sufficient amount of said polymeric emulsion to provide 5 iii; a 4% pick-up. The last formulation contained a sufiicient 3 3 5 TABLE III Water repellency Oil repellency Water IBDQHGIICY Initial Oil repellency after Initial after water Formulation containingrepellency 3 SW 1 DC repellency 3 SW 1 DC First emulsion in 2% OWF formulation 4 4 6 80 80 80 First emulsion in 3% OWF formulation. 6 6 90 80 80 First emulsion in 4% OWF iormulatiom 5 6 6 80 80 80 Second emulsion in 2% OWF formulation. 3 3 3 80 80 80 Second emulsionin 3% OWF formulation 4 4 5 80 80 80 Second emulsion in 4% OWF formulation 5 5 5 90 80 80 amount of said polymeric emulsion to provide a 5% TABLE V pick-up. No. cycles abrasion: Oil repellency Each formulation was applied to 9 oz. sateen, dried 0 and cured as described in Example V. The treated fabrics 500 were tested for their initial oil and water repellency, 1000 their repellency after 15 launderings, and their dynamic 1500 absorption. The results are shown in Table IV following: 5000 EXAMPLE IX Pad baths were prepared with the formulations shown 1 Federal Specifications, Textile Test Methods COCT191BMethod 5500.1. 6American Association of Textile Chemists & Colorists, Method 70B-19 7.
EXAMPLE VII A pad bath was prepared and applied to 8.4 oz./yd. of 100% nylon 66 tricot (commonly used on automobile upholstery) giving 0.22% loading of the fluoropolymer of Example I(c) on weight of fabric. After drying and curing as described in Example V, the fabric had anoil repellency of 6 and a water repellency of 90. After 5,000 cycles in a Wyco abrader, the oil and water repellency were 5 and 50, respectively.
I EXAMPLE VIII ,An emulsion was prepared of the polymer of Example I(c) as described for the preparation of the formulation labeled A in Example III. A cotton/polyester (35/65) poplin fabric was treated with the emulsion, cured for 10 min. at 340 F., given one dry-cleaning, then abraded in a Wyco abrader. Samples were evaluated for oil repellency at various points. The results are shown inTable V.
below. Textiles were padded with these baths and the wet pick-up was controlled to give the concentrations on fabric shown by adjustment of the squeeze rolls. The treated fabrics were then placed in an oven heated at 275 F. for specific times and the indicated repellencies were determined. Fabrics in the oven 40 sec. or less were still wet. In all cases, the fabrics were air dried in a constant humidity room until constant weight is reached before the repellency was determined. The results are shown in Table VI.
FORMULATIONS Percent OWF Component A B C D E Fluoropolymer dispersion A 1 2 Fluoropolymer dispersion B 2 2. 6 3. 6 Fluoropolymer dispersion 0 2. 5 3 5 Permairesh 183 12 12 Catalyst 4 2.3 2.3 2.3 2.3 2.3 Stabilizers 0.04 0.04 0.04 0.04 .04
1 Fluoropolymer dispersion A 6.54% A. I. dispersion of the polymer of example 10 2 Fluoropolymer dispersion B6.21% A. I. dispersion of the polymer of example 1C.
5 Fluoropolymer dispersion C6.21% A. I. dispersion of the polymer of example 20. I
4 Pennafresh 183, catalyst and stabilizer as identified in example III 1 The fabrics treated were:
Fabric A65/ 35 polyethylene terephthalate/cotton- Thermosol dyed poplin.
Fabric B-undyed, mercerized cotton, neutral pH, no whiteners, 1.6 yards/1b., 46 inches wide.
The results are shown below. In these tests, two oil repellency tests were used; 30 sec. refers to Test Method No. 118-1966T as written; 3 mini refers to the 3 minute 15 variation using blue dyed oils described in Example III. Water Repellency was determined as in 'Example III.
Formulation Water repellency On Fabric A, oil repellency develops to a much higher degree before the fabric is actually dry (time 40 sec. or less) with Formulations B and C of this invention than with Formulations D and E which are outside this invention. Likewise, on Fabric B, the water repellency develops more quickly and to a higher degree with Formulation C than Formulation E.
EXAMPLE X A set of cotton/polyester (35/65) poplin fabrics were treated with the formulation described as Formulation B in Example III (which contains the polymer of Example 1(0)), and a second set of the same fabric was treated with a formulation identical to that of Formulation B except that the polymer in Formulation B was replaced with the polymer of Example II(c) (a homopolymer of F(CF ),,CH CH O CCH=CH This second formulation is identified as Formulation B in Table VII below.
Samples of each set of treated fabrics were then subjected to repeated home laundering with tumble dry as described in Example III with the oil repellencies being determined periodically. A second set of samples of each set of fabrics was subjected to the dry-cleaning treatment described in Example HI with oil repellencies again being determined periodically. The results are shown in Table VII.
Home wash-tumble dry. 2 Dry-cleanings.
Notethat Formulation B, where the fiuorinated-polymer contains the durabilizers hydroxyethyl methacrylate and methylolacrylamide is about one oil unit more durable to laundering than Formulation B where the durabilizers are absent. Even when the durabilizers are ab-' sent, reasonable results are obtained. On the other hand, these two added monomers have no beneficial effect on durability to dry-cleaning.
Note that Formulation B is about one oil unit more durable to laundering than Formulation B.
EXAMPLE XI A cotton/ polyester (35/65) poplin fabric was treated with Formulation A of Example III and cured as described therein. The fabric was then subjected to the drycleaning procedure of Example III, omitting the pressing step. Instead, after removal of the excess solvent, the
fabric was placed in a flat bed press for a specified number of seconds on each side of fabric and then the oil repellency was determined. The results are shown in 1 Before dry-cleaning.
Note that oil repellency recovers with essentially no pressing after dry-cleaning.
EXAMPLE XlI Oily soil washability Circular swatches of fabric identical to the fabric used in Example III were treated with the formulations described as follows. Each formulation was identical to that described for the formulations shown in Example 111 except the polymers used in the formulations of Example III Were replaced by the polymers set forth following in the amounts suflicient to provide the on-weight-of-fabric pick-up of polymer set forth following:
The polymer of Example I(a) was used in one formulation in an amount suflicient to provide an OWF pick-up of 1%. The same polymer was used in three other formulations in amounts sufiicient to provide OWF pick-ups of 2, 3 and 4%, respectively. The polymer of Example I( b) was used in four other formulations in amounts sufficient to provide OWF pick-ups of polymer of 1, 2, 3
and 4%. The polymer of Example II(a) was used in four other formulations in amounts sufiicient to provide OWF pick-ups of polymer of 1, 2, 3 and 4 Each treated fabric was soiled by vacuum sucking dyed (blue, oil-soluble dye) Nujol through the cloth. Each fabric was then washed by placing it in an 8 oz. jar with ml. detergent solution (1.5 g./l.) and shaken in a horizontal position in a thermostat bath, at about 50- 55 C. .The samples were then rinsed free of detergent and dried to constant weight. From the weightsof fabric Sample before soiling and after soiling, the percent oil pick-up and percent oil retention, on weight of fabric, were calculated.
A second set of fabrics treated with the formulations described above was first subjected to one home laundering-tumble dry as described in Example III then subjected to the soiling procedure described above. The percent oil retention of each fabric is shown in Table IX following.
TABLE IX 18 hydroxyethyl methacrylate and (d) 0.725 part 60% aqueous N-methylolacrylamide. The resulting polymer Fabric containing polymer or Fabric containing polymer of Fabrics Containing polymer of Example Ia, percent oil retention Example Ib, percent oil retention Example IIa, percent oil retention Formulation Measured with- Measured with- Measured withresulting in OWF out laundering Measured after out laundering Measured after ou t launder ng Measured after pick-up of prior to testing laundering prior to testing laundering prior to testing laundering These results show that the polymers of this invention (1(a) and I(b)) have inherently lower oil retention than does a polymer not of this invention (II(a)).
EXAMPLE XIII Example XII was repeated using two wash temperacient to produce the pick-up on weight of fabric (OWF) shown in Table X below. The fabrics were evaluated only after one home laundering with tumble dry. The results are described in Table X following.
(D) (a) 144 parts F CF CH CH O CCH=CH (b) 16 parts CF CH OCH=CH (c) 0.475 part Z-hydroxyethyl methacrylate, and (d) 0.725 part 60% N- TABLE X Fabric treated 1 with the formula- V Percent 011 tion containing Percent Wash retention the polymer of emulsion, temp., Detergent after one example OWF C. cone., g./l. HWTD v 2 50 0. 42 30 3 50 0. 42 25 2 75 0. 42 23 Ib 3 75 0. 42 12 2 50 1. 5 11 3 50 1. 5 8 2 75 1. 5 7 3 75 1. 5 7
2 50 0. 42 39 3 50 0. 42 34 2 75 0. 42 37 Ha a 75 o. 42 3o 2 50 1. 5 27 3 50 l. 5 25 2 75 1. 5 26 3 75 1. 5 14 I It is readily apparent that under any set of conditions,
EXAMPLE XIV Using the polymerization procedure set forth in Example .I, polymers were prepared using the monomer concentrations set forth in parts A-J. (n in each part is defined as in Example 1(0)).
(A) (a) 132.8 .parts F(CF ),,CH CH O CCH=CH (b) 27.2 parts CF CH OCH=CH (c) 0.475 part 2- methylolacrylamide. The resulting polymer contained 1.25% (d), by weight.
(E)(a) 144 parts F(CF ),,CH CH O CCH=CH (b) 16 parts CF OCF=CF (c) 0.095 part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60% aqueous N- methylolacrylamide. The resulting polymer contained 0.25% each of (c) and (d) by weight.
(F )(a) 130.9 parts F(CF CH CH O CCH=CH (b) 29.1 parts CF OCF CF (c) 0.095 part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60% N-methylolacrylamide. The resulting polymer contained 92.9% (a), 6.6% (b), 0.25% (c) and 0.25% (d), by weight.
(G) (a) parts F(CF ),,CH CH O CCH%I-I (b) 40 parts CF OCF=CF (c) 0.095 part Z-hydroxyethyl methacrylate, and (d) 0.145 part 60% N-methylolacrylamide. The resulting polymer contained 0.25% (c) and (d) each, by weight.
(H) (a) 144 parts F(OF ),,CH CH O CCH=-CH (b) 16 parts CF (CF OCF=OF (c) 0.095 part Z-hydroxyethyl methacrylate, and (d) 0.145 part 60% N-methylolacrylamide. The resulting polymer contained 0.25 (c) and ((1) each, by weight.
(I) (a) 130.9 parts F(CF CHgCH O CCH=CH (b) 29.1 parts CF (CF OCF=CF (c) 0.095 part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60% N- methylolacrylamide. The resulting polymer contained 0.25% (c) and (d) each, by weight.
(J (a) 120 parts F(CF ),,CH CH O CCH=CH (b) 40 parts CF (OF OOF=CF (c) 0.095 part 2-hydroxyethyl methacrylate and (d) 0.145 part 60% N- methylolacrylamide. The resulting polymer contained 0.25% (c) and (d) each, by weight.
Each polymeric emulsion obtained in parts A] above was diluted to an emulsion containing 6.21% active ingredient of the polymer to obtain formulations resulting in percent pick-up of each polymer of 1, 2 and 4% on weight of fabric ('OWF). Each formulation also contained 12% OWF of the crease-proof resin that was used in the formulations of Example III, 2.3% OWF of the catalyst that was used in the formulations of Example IH, 0.05% OWF of the stabilizer that was used in the formulations of Example 111, and in addition, contained 0.4% OWF acetic acid.
Each formulation was applied to the fabric used-in Example III as described therein and cured and tested for oil repellency as described therein. The results are shown below in Table XI.
A. Example Ia was repeated using (a) 144 parts F(OF ),,CH 'CH O CCH=CH (defined as in Example I(c)), (b) 16 parts CF CH OCF=CF (c) 0.095 part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60% N rnethylolacrylamide The resulting polymer contained 0.25% (c) and 0.25% (d), by weight.
B. Example Ia was repeated using (a) 131.2 parts F(CF ),,CH CH O CCH=CH (defined as in Example I(c)), (b) 28.8 parts CF CH OCF=OF (c) 0.095 part Z-hydroxyethyl methacrylate, and (d) 0.145 part 60% N- methylolacrylamide. The resulting polymer contained 0.25% (c) and 0.25% (d), by weight.
The emulsions obtained in these two polymerizations were diluted to 5.4% A1. of
incorporated into the formulation of Example XIV and applied as in Example XIV with the results shown in Table XII.
TABLE XII Repellencies Cone, Polymer percent Initial 1 HWAD 1 HWTD 1 DC example OWF oil oil oil 011 l 2 l 1 XV A 2 2 4 4 4 6 3 5 5 1 3 0 2 p 2 XVB 2 5 2 4 5 4 6 3 5 5 EXAMPLE XVI Using the procedure of Example XII, oil retention was determined for a number of polymers of the previous examples. All of these polymers were applied as described in Example XII. The results are shown in Table XIII.
TABLE XIII Percent Percent oil Polymer example OWF retention EXAMPLE XVII Bleached, unsized paper was immersed in an aqueous dispersion containing 0.25 by weight of the polymer of 2 .20 2. Example I(c) for 15 'sec., passed through a'nip roll (120% wet pickup) and dried for three minutes at C. The resulting paper contained 0.3% by weight p y The resulting paper Withheld the No. 5 oil (dodecane) from oil repellency test No. 118-1966T mentioned in Example III from penetration of the paper for three minutes. A lactic acidlink mixture failed to penetrate for about one minute.
Similarly, unbleached waterleaf kraft paper was treated to obtain 0.4% fiuoropolymer on weight of paper. The No. 8 oil (heptane) failed to penetrate after three minutes and the lactic acid/ink mixture required five minutes for penetration.
The preceding.representativeexamples may be varied within thescope of the present total specification disclosure, as understood andpracticed by one skilled in the art, to achieve essentially the same results.
The foregoing detailed description has been given for clear ness of understanding only .andno unnecessary limitationsare to be, -understood therefrom. The invention. is
not limited to the exactdetails shown and described, for obvious modifications willoccur to those skilled in the art.
1. An oiland water-repellent copolymer consisting essentially of (a) from about 75 percent to about 98 percent by weight of units derived from monomers of the structural formula wherein R is a perfluoroalkyl group of from four to fourteen carbon atoms; I M 1 (b) from about 25 percent to about 2 percent by weight of units derived from monomers selected from the class consisting of 1) ROCH=CH wherein R is X(CF CH or (CF CH where X is F or H and n is one or two, or p (2) R0CF=CF wherein R" is F(CF or R where m is from one to three; and (c) from 0 percent to about 5 percent by weight of units derived from monomers selected from the class consisting of 1 (1) CH =CR CONHR OH, (2) CH =CR CO R QH, (3.) CH CR CO R or (4) mixtures of the above wherein R is H or CH R is alkylene of one to four carbon atoms, R is alkylene of two to four carbon atoms, and R is epoxyalkyl of three to four carbon atoms;
.present ina weights ratio of 35/30/18/8/3.
4. The copolymer of claim 3, said copolymer having'an inherent viscosity: as 0.5% solutions'in trichlorotrifluoroethane at 30 C. of less than 0.8. 2 I
5. The copolymer of claim 4 wherein the units defined in part (b) are derived from'ROCH=CH 6. The copolymer of claim 5 wherein the R group of ROCH=CH is CF CH I 7. The copolymer of claim 1 wherein the units defined in part (b) are derived frorri'ROCH=CH 8. The copolymer of claim 7, said copolymer having an inherent viscosity as 0.5% solutionsin trichlorotrifluoroethane at 30 C.'of less than 0.8. 2
9. The copolymer of claim 8 wherein the R group in ROCH=CH is CF CH 21 10. An oiland water-repellent copolymer consisting essentially of (a) from about 75 percent to about 98 percent by weight of units derived from monomers of the structural formula wherein R: is a perfiuoroalkyl group of from four to fourteen carbon atoms;
(b) from about 25 percent to about 2 percent by weight of units derived from monomers selected from the class consisting of 1) ROCH=CH wherein R is X(CF CH or (CF CH- where X is F or H and n is one or two, or
(2) ROCF CF wherein R is 1 (CF or R where m is from one to three; and
wherein the total percent by weight of units present in the copolymer is 100 percent.
11. The copolymer of claim 10 wherein R in the units defined in part (a) of claim 10 has the formula F(CF wherein s is a cardinal number of four to fourteen.
12. The copolymer of claim 11 wherein s in the formula F(CF has the numerical values 6, 8, 10, 12 and 14 present in a weight ratio of 35/ 30/ 18/ 8/ 3.
13. The copolymer of claim 12, said copolymer having an inherent viscosity as 0.5% solutions in trichlorotrifiuoroethane at 30 C. of less than 0.8.
14. The copolymer of claim 13 wherein the units defined in part (b) are derived from ROCH=CH 15. The copolymer of claim 14 wherein the R group of is CF3CH2.
16. The copolymer of claim 10 wherein the units defined in part (b) are derived from ROCH=CH 17. The copolymer of claim 16, said copolymer having an inherent viscosity as 0.5% solutions in trichlorotrifluoroethane at 30 C. of less than 0.8.
18. The copolymer of claim 17 wherein the R group of ROCH=CH is CF CH 19. A textile fabric treated with the copolymer of claim 1.
20. A textile fabric treated with the copolymer of claim 10.
21. Paper treated with the copolymer of claim 1.
22. Paper treated with the copolymer of claim 10.
References Cited UNITED STATES PATENTS 2,991,277 7/1961 Schildknecht 260-861 3,102,103 8/1963 Ahlbrecht et al 260-861 3,282,905 11/1966 Fasick et a1 26086.1 3,347,812 10/1967 De Marco et al. 260-861 3,378,609 4/1968 Fasick et al 26086.1 3,384,627 5/1968 Anello et al 260-86.1 3,459,696 8/1969 Read 260-861 HARRY WONG, JR., Primary Examiner U.S. Cl. X.R.
PEI-1050 UNITED STATES PATENT OFFICE 69 CERTIFICATE OF CORRECTION Patent No. LEQJBZ Dated December 8. 1970 Inventor-(s) Ibgmag K, may Jr.
In claim p (1), a single bond should follow the formula X(CF CH and should appear x(g 2)nc 2 In claim 1, part (4), "wherein R should pertain to all of the claim, -not onl; "mixtures of the above".
In claim 10, part (1), a. single bond should follow the forum X(CF CH and should appear as I(CF CH Signed and sealed this 23rd day of March 1 971 (SEAL) Attest:
EDWARD M.FLETCHER,JR. WILLIAM E. SGHUYLERJR. Attesting Officer Commissioner of Patents
US3546187A 1969-03-10 1969-03-10 Oil- and water-repellent polymeric compositions Expired - Lifetime US3546187A (en)
US80581469 true 1969-03-10 1969-03-10
US3546187A true US3546187A (en) 1970-12-08
ID=25192572
US3546187A Expired - Lifetime US3546187A (en) 1969-03-10 1969-03-10 Oil- and water-repellent polymeric compositions
US (1) US3546187A (en)
BE (1) BE747060A (en)
DE (1) DE2011316B2 (en)
FR (1) FR2037897A5 (en)
GB (1) GB1261867A (en)
EP0109171A1 (en) * 1982-10-13 1984-05-23 Minnesota Mining And Manufacturing Company Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith
US20170088653A1 (en) * 2009-03-25 2017-03-30 Daikin Industries, Ltd. Surfactant comprising fluorine-containing polymer
US2991277A (en) * 1955-06-10 1961-07-04 Air Reduction Copolymers of trifluoroethyl vinyl ether and alkyl esters of acrylic of methacrylic acid, and method for preparing same
GB1261867A (en) 1972-01-26 application
FR2037897A5 (en) 1970-12-31 application
DE2011316B2 (en) 1972-03-02 application
BE747060A (en) 1970-08-17 grant
DE2011316A1 (en) 1970-10-01 application
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