CA1220891A - Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith - Google Patents

Abstract

Abstract of the Disclosure 1-Halomethyl-2-alkoxyethyl acrylates and methacrylates useful for making acrylate and methacrylate polymers and copolymers. Preferred monomers are used to prepare fluorochemical copolymers which impart oil and water repellency to cellulosic materials and textile fibers. The fluorochemical copolymers are derived by weight) from about 1 to 30% of the preferred monomers, 60 to 80% fluorochemical acrylate, 1 to 15% glycidyl acrylate or methacrylate, 1 to 6% of certain cationic acrylates or methacrylates, and 0 to 20% vinylidene chloride.

Description

6~

FLUOROC~E~IICAL COPOLYMERS AND OVENABLE
PAPERBOARD AND TEXTILE FI~ERS T~~TED THEREWITH

Technical Field This invention relates to fluorochemical copolymers which impart high temperature oil and water repellency and food stain resistance to cellulosic materials. This invention also relates to fluorochemical copolymers which impart oil and water repellency to textile fibers. Also, this invention relates to internal ("wet-end") beater additives useful in the manufacture of ovenable paperboard In addition, this invention relates to fluorochemical copolymer-treated cellulosic materials and shaped articles made therefrom (e.g., ovenable paper-board cartons and trays), copolymer-treated textile fibers (e.g., carpet fibers), and processes for making the same.

Background Art Various fluorochemical wet pick-up and internal sizing agents for paper treatment are described, for example, in Rengel and Young, "Internal Sizing of Paper and Paperboard", Tappi monograph series number 33, pp. 170-189 (1971), Colbert~ "Fluorochemicals-Fluid Repellency for Non-woven Substrates", Tappi, The Journal of the Technical Association of the Pulp and Paper Industry, 59, 9, .
(September, 1976), Banks, ~d., Organofluo ine Chemicals and their Industrial Applications, pp. 231-234 (1979), and Schwartz, "Oil Resistance Utilizing Flu~rochemicals", Tappi conference preprint, 1980 Sizing Short Course, Atlanta, Georgia~ Several fluorochemical phosphates have been approved by the United States Food and Drug Administration for use on paperboard in direct contact with Eood for human consumption. These fluorochemical phosphates can be used as wet pick-up or as internal treatments. They primarily provide oil resistance, and are used on paper plates, bags for bakery goods, cartons and -trays for oil fried foods (eOgO, French fries), and in bags and cartons for pet foods.
The advent in recent years of the microwave oven has created a need for non-rnetallic containers for cooking or food-warminy which have resistance to both oily and aqueous foods at oven temperatures, since metallic containers (e.g., aluminum trays) do not efficiently cook foods in microwave ovens and ~nay promote electrical arcing i~ the metallic container walls approach or touch the walls of the microwave oven. A suitable non-metallic food container should also withstand free~ing temperatures and conventional oven temperatures because foods sold in such containers will often be frozen and will be cooked in both microwave and conventional ovens~ Cooking times for foods stored in such containers usually range from a few minutes to sixty minutes or more, and cooking temperatures usually range from about 95~C to ~40 ~C or higher.
Existing commercially available fluorochemical phosphate sizing treatments do not provide sufficient high temperature water repellency to ovenable paperboard food trays exposed to cooking conditions for extended periods of time. Food packagers have had to employ other container materials or constructions to obtain adequate ovenability.
For example, formed food trays can be made entirely from plastics such as polyeth~lene terephthalate. Also, laminated, stamped food trays can be made from a layer of conventional paperboard coated on the food side with a thin ~0.25 to 0.33 millimeters) film of extruded polyester.
Food containers made entirely from plastic are relatively expensive, consume scarce petroleum resources, and lose rigidity at elevated temperatures. Food containers made from laminated paperboard and polyester sheets can become stained with oil on the unprotected outside surface (e.g., during food filling operations), are prone to rupture of the container at corners during tray-forming operations (due in part to differences in moisture content within the paperboard sheet), are susceptible to delamination when -3~

foods are heated to very high temperatures (e.g., when bacon or sausage are heated in microwave or conventional ovens), and are relatively expensive, re~uiring about 110 grams o~ polyester resin per kilogram of paperboard. In addition, scrap or waste paperboard from tray forming or other operations performed on paperboard/polyester laminate is not repulpable, and this scrap is sometimes as much as 25 percent of the total paperboard/polyester laminate consumed.

Disclosure of Invention The present invention provides, in one aspect, fluorochemical copolymers useful for imparting oil and water repellency under foo~ cooking conditions to cellu-losic materials, or oil and water repellency to textile fibers, said copolymers comprising ~by weight):
(a) 60 to 80~ of polymer chain repeat units derived from fluoroacrylate monomer of the formula:

(Rf)pQOCOCH=CH2 wherein Rf is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalen-t organic connecting group, and p is 1 or 2;
~b) 1 to 30% of polymer chain repeat units derived from alkyl or alkoxyalkyl acrylate or meth-acrylate monomer of the formula:
Rlo(R2o)n[c(o)cH2o]mcocR3=cH2 II

wherein Rl is a Cl_20 alkyl or cycloalkyl group, R2 is a Cl_6 alkylene group, each R2 group can be the same as or different from other R2 groups, n is zero to 10 with the proviso that when n is zero Rl is a Cl_l6 alkyl or cycloalkyl group, m is zero or 1, and R3 is H
or methyl;

~4~ ~2~
(c) 2 to 15% of polymer chain repeat units derived ~rom monomer of the formulao o CH2C~ICH2OCOC(R4)=CH2 III

wherein R4 is H or methyl;
~d~ l to 6~ of polymer chain repeat units derived from cationic monomer of the formula:

CH2=C(~5)ZY~X- IV

wherein R5 is H or methyl, Z is a divalent electron withdrawing group which activates free radical poly-meri~ation, Y+ is a monovalent cationogenic group, and X~ is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride;
15 with the proviso that the weight percent of carbon-bonded fluorine in said copolymers is at least 15~.
The present invention also provides cellulosic materials and textile fibers which have been treated with said fluGrochemical copolymers, shaped articles (e.g., food 20 trays~ made from such treated cellulosic materials, and articles (e.g.~ carpet) made from such treated fibers.
In addition, the present invention provides a process for imparting high temperature oil and water repellency and food stain resistance to cellulosic 25 materials/ comprising the step of applying to said materials at least one o~ said fluorochemical copolymers.
Also, the present invention provides a process for imparting oil and water repellency to textile fibers, comprising the step of applying to said fibers at least one 30 of said Eluorochemical copolymers.

Detailed Description The copolymers of the present invention will be construed to include not only copolymers actually prepared 5~

from the above-named monomers, but also copolymers which were not actually prepared from such monomers but whose chemical structures are such that the copolymer could have been prepared from such monomers if desired.
The Rf substituent of the monomers of Formula I
is a monovalent, fluorinated, aliphatic, preferably saturatedr organic radical haviny at least three carbon atoms and as many as twenty carbon atoms. The skeletal chain of Rf can be straight, branched, or, if sufficiently large, cyelier and can include catenary divalent oxy~en a~oms or trivalent nitrogen atoms bonded only to carbon atoms. Preferably, Rf is fully fluorinated, but carbon-bonded hydrogen or chlorine atoms can be present as substi-tuents on the skeletal chain of Rf, provided that not more than one atom of either hydrogen or chlorine is present for every two carbon atoms in the skeletal chain of Rf, and Eurther provided that Rf contains at least a terminal perfluoromethyl group. While Rf radicals containing a large number of carbon atoms will function adequately, raclicals containing not more than about 14 carbon ato~s are preferred since larger radicals usually represent a less efficient utilization of fluorine than is possible with smaller radicals. Preferably, R~ has an average of about 6 to 10 carbon atoms.
Q is an organic polyvalent (e.~., divalent) acyclic or alicyclic radlcal of 1 to about 12 carbon atoms, or a polyvalent (e.g., divalent) aromatic radical of about 3 to 12 carbon atoms. Q can contain, for example, skeletal nitrogen, oxygen, or sulfur atoms, or carbonylimino, sulfonylimino, imino, or carbonyl radicals. Q is unsub-stituted or substituted by halogen atoms, hydroxyl, alkyl, or aryl radicals, and preferably is free from aliphatic unsaturation. Suitable Q radicals incluc~e -CH2-, -C2H4-, -C4H8-, -C6H4-, -C6H3<, -CH2C6H4C~2-, ~C2H4SC2H4-, -C2~I4OC4H8-, -C~2OC2H4-, -SO2N(R6)C2H4-, -CON(R6)C2M4-, -C3H6CON(R6)C2H4-~ -C2H4N(R6)c2H4-~ -COOCH2C(CH3)~CH2-, -SO2N(R6)CH2CM(CH3)-, and -C2H4SO2M(R6)C4H8-, where R6 is H

~2~

or a Ci_4 alkyl radical. Preferably, Q is -CEl2-, -C2H4-, or -so2N(R6)c2H4-.
Preferably, the monomers of Formula I contain at least about 30 weight percent fluorine and more preferably about 40 to 60 ~eight percent fluorine. Preferably, about 65 to 75 weight percent of the monomers of Formula I are used to form the copolymers of this invention.
Representative monomers of Formula I include C8Fl7so2N(cH3)cH2cH2ococH=cH2~
C6Fl3c2H4sc2H4ococH=cH2~ C2F5c6FlocH2ococH=cH2~
C7Fl5cH2ococH=cH2~ C7F15CON(CH3)C2H4OCOCH CH2 (CF3)2CF(CF2)6CH2CH(OH)CH~OCOCH=CH2, (cF3)2cFo~2F4c2H4ococ~=cH2 C8Fl7c2H4sO2Nlc3H7)c2El~ococH=cH
C7Flsc2Ef4coNHc4HgococH=cH2~ C3F7~CFCF2)2fFCH2CCFI=

C8 Fl 7S02N ( C2H5 ) C4H80COCH=CH2, (C3F7)2c6H35o2N(cH3)c2H4ococH=cH2~
~CF2CF,~
C2F5-CF /NcF2cF2coN(cH3)c2H4ococH=cH2~ and C8Fl7cF=cHcH2N(cH3)c2H4ococH=cH2.
In the monomer of Formula II, Rl is straight chain, branched, or cyclic, e.g., CH3(CH2)8CH2-~
CH3(CH2)3-~ CH3(CH2)4CH(C2Hs)CH2-, or C6Hll-. Rl preferably is a Cl_4 alkyl radical, and most preferably is CH3- or CE13CH2-. R2 is straight chain or branched, e.g., -C2H4-, -(CH2)4-, or -CH2CH(CH3)-. R2 preferably is a Cl_4 alkylene radical, and most preferably is -C2H4-.
Preferably n is 1, and preferably m is zero. Also, R3 preferably is H. Preferably, about 10 to 20 wei~ht percent of the monomers of Formula II are used to form the copolymers of this invention.
Representative monomers of Formula ~I include the acrylate monomers CH3OCOCH=CH2, C2H5OCOCH=CH2, C~HgOCOCH=CH2~ CH3(CH2)gCH2OCOCH=CH2, CH3(CH2)4CH(C2Hs)CH2OCOCE~=CH2, CH3OCH2OCOCH=CH2, 3 2 4 COCH C~2~ CH3oc4~8ococ~=cH2~ C2H5OC2~ COCH=CH2~
2H5~)C3~60COCH-CE12, C2H5( C2H4) ~CCH= cH2 ' C2~150C2Ha~OC ( O ) C1~20COCH=CH2 ~ C2~50 ( C2H40 ) ~C ( O ) CH20COCE~=CH
~H9O(C2~l4O)2COCH=C~12, C2H5OCH2CH(Ci~3)OCOCH=CH2, and C2H5O(CH2C~(CH3~)2OCOCH=C~l2, as well as the methacrylate monorners corresponding thereto The monomers of Formula II can be prepared using conventional methods. Monomers in which n and m are zero can be prepared, for example, by reacting an alkanol (e.g., ethanol) with acryloyl chloride, methacryloyl chloride, acrylic acid, or methacrylic acid to form an ester.
Monomers in which n is 1 or more and m is zero can be prepared, for example, by reacting an alkanol with an alkylene oxide (e.g., e-thylene oxide), and reacting the resulting adduct with the above named acid chlorides or acids. Monomers in which m is 1 can be prepared, for example, by reacting an alkanol (for monomers where n is zero) or the above-described adduct of alkanol and alkylene oxide (for monomers where n is 1 or more) with chloroacetic acid, and combining the product of the latter reaction with the above-named acid chlorides or acids The above-described syntheses are generally carried out in the presence of sui-table catalysts, e.g. an acid catalyst for esterification with acrylic or methacrylic acid or an amine catalyst for es~erification with acryloyl or methacryloyl chloride. For any of the above-described syntheses, the -final product should be purified (e~g~l by distillation, acid wash, or base wash) to remove residual acid, acid chloride, catalysts~ and other impurities or by-products.
In the monomers of Formula III, R~ preferably is methyl. Preferably, about 3 to 10 weight percent of the monomers of Formula III are used to Eorm the copolymers of this invention.
In the monomer of Formula IV, the Z group has a carbonyl or aromatic group or an oxygen or sulfur atom ~;~2~

bonded directly to the vinylidene group of the monomer.
The Z group can be, for example, -COO(CH2)p-, -CO(CH2)p-, -CONH(CH2)p-, -OCO(CFl2)p-, -0(CH2)p-, -S(c~2)p-~ -C6H4-~ or -C6H4(CH2)p-, where p is l to lO. The polymethylene moiety -(CH2)p- and the aromatic moiety -C6H~- in such structures can be substituted ~ith substituent ~roups or atorns which do not interfere with free-radical polymeri~ation, such as alkyl, aryl, or hydroxyl groups or halogen atoms. The R5 group preferably is CH3-. The Z group preferably is selected from -COOCH2CH(OH)CH2-, -COO(CH2)k-, or -CONH(CH2~1~-, where ~ is 2 to 6. Useful Y~ groups include (a) the pyridinium iOn +N ~ , (b) the ion N+(R7)3 where each R7 independently is H or a Cl_4 alkyl group, or where any two of R7 combine to form an alkylene group having 4 to lS 5 chain carbon atoms, or any two of R7 are ~CH2)2- and combine with an oxygen atom to form the moiety ~CFl2)20(CH~)2-, (c) phosphonium ions, and (d) sulfonium ions. Preferably, Y+ is N+(R3)3 where each R~ indepen-dently is a Cl_4 alkyl group. The anion X~ is a matter of choice, and ordinarily is selected based upon the method of synthesis of the cationic monomerO ~~ preferably is selected from halide ions such as Cl-, Br~, I-, and alkyl sulfate ions such as CH30S03-. Preferably, about 2 to 4 weight percent of the monomers of Formula IV are used to form the copolymers of this invention.
Representative monomers of Formula IV incl~de CH2=C(CH3)COOC2H4N+(CH3)3 Cl-, CH2=CHCOOC2H4N+(CH3)3 Cl , CH2 C~CH3)COOC2H4N+(CH3)3 -OS03CH3, CH2=C(CH3)COOCH2CH(OH)CH2~+(CH3)3 Cl-, CH2=c(cH3)coNHc3H6N+(cH3)3 Cl CH2=c(cH3)cooc2H4N (C2~5)2H Cl CH2=c(cH3)cooc2H4l (C2H5)2 I ~
c~3 CH2=CHCOOCH2CH2N\ ~ Br~, CH2=CHOC3H6N \ ¦ Br~, and ~ CH3 CH2cf~2 CH2=CHC6H~CH2N+(CH3)3 Cl--~ he performance of paperboard, or of -textile fibers, which have been treated with the fluorochemical copolymers of this invention is affected, in part, by the types and amounts of monomers from which the fluorochemical copolymers are derived. For example, use of increased amounts of the monomers of Formula I or Formula II tends to enhance oil and water repellency of the trea-ted paperboard or textile fiber. Use of increased amounts of the monomer of Formula III tends to enhance water repellency, but can detract from oil repellency. Use of increased amounts of the monomer of Formula IV tends to enhance efficient deposition of the fluorochemical copolymer onto cellulosic or textile fibers. Also, this latter monomer aids in emulsifying the fluorochemical copolymer and in stablizing lS the emulsion in which the copolymer can be prepared, there-by enabling the use of reduced levels of other emulsifiers.
Vinylidene chloride, if used, tends to enhance water repellency, and serves as a compatible "filler" monomer in the fluorochemical copolymer. Where higher weight percen-tages of the monomer of Formula II are used, then lesseramounts of vinylidene chloride are required, enabling the amount of vinylidene chloride to be reduced to zero if desired.
Minor, non-interfering amounts of monomers other than those described above can also be incorporated into the fluorochemical copolymers of -this invention. For example, the fluorochemical copolymers of this invention can contain up to about 10 weight percent of polymer units derived from ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene fluoride, vinyl chloroacetate, acrylonitrile, vinylidene cyanide, styrene, alkyl styrenes, halogenated styrenes, methacrylonitrile, N-vinylcarbazole, vinylpyridine, vinyl alkyl ethers, vinyl alkyl ketones, butadiene, chloroprene, fluoroprene, isoprene~ and mixtures thereof. ~owever~ the presence of such monomers is not required, and useful fluorochemical copolymers of this invention can consist of or consist essentially of polymer ~2,~

chain repeat units derived from the monomers of Formulae I, II, III, and IV~
Non-interfering amounts of, for example, fluoro-chemical methacrylatesl Eluorochemica:l alkoxyalkylmeth-acrylates, C18 or longer alkyl acrylates or methacrylates,acids such as acrylic acid, methacrylic acid, or chloro-acetic acid (most particularly acrylic acid), or hydroxyl containing vinyl monomers (particularly those containing terminal hydroxyl functionality, such as N-methylolacryl amide and 2-hydroxyethyl acrylate~ can be incorporated into the copolymers of this inven-tion, but the use thereof pre-ferably is avoided, as their presence in the copolymers of this invention detracts from the oil and water repellency of paperboard or textile fiber treated therewith.
The fluorochemical copolymers of this invention can be prepared using known techniques for emulsion or solution polymerization. Emulsion polymerization is pre-ferred, and can be carried out on a batch or continuous basis in a reaction vessel equipped with a stirrer and external means for heating or cooling the feedstocks and vessel contents. Typically, the reaction vessel will contain about 5 to 50% by weight of the monomers which will be polymerized together, about 35 to 80 percent by weight water, about ~ero to 30 pereent by weight of polar organic solvent(s), and about Ool to 10 percent by weight oE
surface-aetive agent(s) (i.e., emulsifying agents) capable of stablizing the resulting emulsion. The reactants are heated to about 40 to 90C, preferably about 65 to 75C.
Generally about 0.1 to 2 weight percent (based upon the weight of the monomers whieh will be polymerized together) of a suitable catalyst and about 0.1 to 0.8 weight percent (on the same weight basis) of a suitable chain transfer agent is included in the reaction mixture. ~t the comple-tion of the reaction, the polar organic solvent preferably is stripped off, e.g., by evaporation. The product is filtered and is then ready for use a

2~

Suitable polar or~anic solvents include acetone, ethanol, methanol, and other solvents such as those described in U.S. Patent No. 3,062,765. Acetone is a preferred solvent~ Suitable em~lsifyincJ agents include cationic surface active agents such as dodecyltrimethyl-ammonium acetate, octadecylmethyl bis(polyoxyethyl) ammonium chloride, hexadecyltrirnethylammonium bromide, trimethyloctadecylammonium chloride, benzyldodecyldirnethyl-ammonium chloride, and N-~2-(diethylamino)ethyl]-oleamide hydrochloride. Suitable emulsifyin~ agents also include non-ionic surface-active agents such as the condensation products of ethylene oxide with compounds such as hexyl-phenol, isooctylphenol, hexadecanol, oleic acid, C12_15 alkanethiols and C12_18 alkyl amines. Suitable catalysts include 2,2'-azobis(isobutyramidine) dihydrochloride, potassium persulfate, and other water-soluble catalysts known to those skilled in the art. 2,2'-Azobis(isobutyr-amidine) dihydrochloride is a preferred catalyst. Suitable chain transfer agents include alkanethiols having 4 to 12 carbon atoms and chain transfer solvents (which can simul-taneously function as polar organic solvents during the formation o the fluorochemical copolymer) such as isopro-panol. A preferred chain transfer agent is n-octanethiol.
For batch polymerization, lowering the solids content in the reaction vessel will improve the yield of copolymer. Mild agitation of the reactants will tend to increase copolymer yield and decrease the oil and water repellency of paperboard or textile fiber treated with such copolymer. More severe agitation of the reactants will tend to decrease copolymer yield and increase the oil and water repellency of paperboard or textile fiber treated with such copolymer.
Solution polymerization is less preferred than emulsion polymerization. I~ solution polymeri~ation is

3~ employed, the cationic monomer of Formula IV preferably is replaced by a tertiary amine-containing vinyl monomer which is copolymerizable with the other monomers of the reaction -12 ~ 8~

mixture. After copolymer formation, the tertiary amino groups of ~he copolymer are quaternized (e.g., at room tempera-ture) to introduce cationic ammoniuM groups into the copolymer.
In order to prepare treated paperboard, the fluorochemical copolymers of this invention preferably are applied as internal (i.e., "wet-end"~ additives to an aqueous suspension oE cellulosic Eibers, using conventional papermaking equipment. Alum content of the furnish preferably should be kept at low levels, as high alum content can cause the treated paperboard to have reduced oil and water repellency. The fluorochemical copolymer preferably is added at or upstream from -the headbox of the papermaking machine, and preferably is added at the headbox. Orc3inarily, a polymeric cationic retention aid is added to the stock prior to addition of the fluorochemical copolymer, in order to limit loss oE the fluorochemical t' .. ~ copolymer into the whitewater. Suitable retention aids include resins such as "Betz~1275" (commercially available from Betz Laboratories, Inc.) or i'Reten 304" (commercially available from Hercules, Inc.), both of which are believed to be polymeric cationic aliphatic amides derived from adipic acid and diethylene triamine. Preferably, at least about 80 to 3~ percent ~luorochemical copolymer retention is obtained at an addition level of about 0.1 to 2 percent retention aid solids based on the weight of fibers.
Adjuvants such as dyes, inhibitors, antioxidants, sizing agents, emulsifiers, and the li~e can be added to the fluorochemical copolymer if desired.
The fluorochernical copolymer is added to the furnish in amounts sufficient to provide the desired level of oil and water repellency. In general, these amounts are between about 0.2 to 2 percent fluorochemical copolymer based on weight of fibersO F'or reasons of economy, it is preferred to employ a low level of fluorochemical copolymer, coincident with attainment of adequate oil and water repellency in the finished paperboard product.
trR~

Following addition oE the fluorochemical copolymer, the furnish is processed using conventional papermaking technology.
Treated paperboard can also be prepared by S applying the fluorochemical copolymers of this invention using wet pick-up methods, such as a size press or calendar stack. If desired, sequential internal and wet pick-up application of the fluorochemical copolymers of this inven-tion can be employed Some paperboard made in accordance with this invention attains maximum water repellency after aging (see, e.g., the treated paperboard of Example 2, below).
Little or no aging will be required for rnany other fluoro-chemical copolymers exemplified below.
Treated paperboard of this invention can be formed into containers (e.gD, trays) using conventional techniques (e.g., the "Sprinter", "Kliclok", "Peerless", or molded pulp methods~. Because internally-applied fluoro-chemical copolymers of this invention penetrate uniformly throughout the paper web, aggressive die stamping, folding, or creasing of the treated paperboard will not expose untreated fibers, and the oil and water repellency of the treated paperboard will not be materially lessened by tray-forming operations. Also, if a moisturizing step is used during container-forming, the treated paperboard of this invention will have a more uniform moisture content than moisturized paperboard/polyester laminates, enabling the treated paperboard of this invention to be more readily formed into containers without rupture thereof. In con-trast to the use of paperboard/polyester laminates, thetreated paperboard of this invention does not tend to stick to the heated steel dies used in press-forming tray manufacturing operations. Both sides of the treated paperboard of this invention readily receive printing in~.
In contrast/ it is difficult to perform printing operations upon the polyester side of paperboard/polyester laminates.
In addition, scrap treated paperboard of this invention -14~

which is left over from the container-forming operation can be repulped and reused, unlike scrap from container-forming operations employillg paperboard/polyester laminates.
The treated paperboard containers of this inven-tion can be filled with food and stored usiny conventionaltechniques. Cooking of food in such containers is also carried out in conventional fashiont but the elevated high temperature ~il and water repellency of the paperboard containers of this invention will enable use of high temperatures (e.g., 230~C), long cooking times (e.g., two hours or more), and cooking of foods (e~g., spinach~ which have been prone to cause oil or water staining in paper-board containers heretofore employed.
The fluorochemical copolymers of this invention have also been found to be useful for imparting soil resistance and oil and water repellency to textiles (e.g., polyester carpet fibers). The fibers (or yarn) can be treated as such or in an aggregated form (e.g., skein or roving) with the fluorochemical copolymer, or the fabricated textile (e~g., articles such as carpet and woven fabrics) can be treated with the fluorochemical copolymer.
The treatment can be carried out by applying the fluoro-chemical copolymer by known techniques customarily used in applying fluorochemicals to fibrous substrates. For example, the treatment can be carried out by immersing the fibrous substrate in a bath containing the fluorochemical copolymer, padding the substrate or spraying the same with the fluorochemical copolymer, by using foam, kiss-roll, or metering applications (e.g., spin finishing), or by exhaus-tion of the copolymer onto the substrate in a dyebath. Ifdesire~, the fluorochemical copolymer can be co-applied with adjuvants, e~g., arltistatic agents or fiber lubricants.
For textile application dependent on substantial exhaustion of the fluorochemical copolymer from the treating medium, the concentration of copolymer in the exhaustion bath generally will be about 0.001 to 0.1 weight percen-t. For applications not involving exhaustion, e.g., -15~

padding, spraying, etc., higher concentrations will be needed. The amount of fluorochemlcal coE)olymer deposited on the treated textile irrespective of the particular mode of application will be, Eunctionally speaking, sufEicient to impart the desired degree o~ oil and water repellency, and generally this amourlt will be 0.02 to 3, preferably 0.05 to 0.16 weight percent, or, expressed in terms of fluorine content, 0.01 to 1.5, preEerably 0.03 to 0.08 weight percent fluorine.
The followiny examples are offered to aid understanding of the present invention and are not to be construed as limiting the scope thereof.

Preparation of Copolymer Emulsion The following ingredients were placed in a screw-capped, 115 ml glass bottle, in the amounts set forth below in Table I:
TABLE I
Ingredient Amount, g 20 C8~l7so2NtcH3)c2H4ococH=cH2 21.0 C2H50C2H40COCH=cH2 /o~
CH2CHCH2OCOC(CH3)=CH2 1.5 C~2 C(CH3)COOC2H4N+(CH3)3 Cl-(a) 1.2 25 n-octanethiol 0.06 C18H37N (CH3~(c2~4o)x}l(c2H4o)yH Cl , x+y=lS(b) o,g 2~2'-Azobis(isobutyramidine) dihydrocllloride(C) 0.15 Deionized water 52.5 Acetone, reagent grade 17.5 (a) "Sipome ~Q-6-75", commercially available Erom Alcolac, Inc.
(b) "Ethoquad~18/25", commercially available from Armak Ind-~strial Chemical Division of Akzona, Inc.
(c) "V50", commercially available from Crescent Chemical 35Co.
r~ k The glass bottle and its contents were briefly subjected to reduced pressure to remove oxy~en. The glass bottle was then flushed with oxygen-free nitrogen, sealed, placed in a water bath maintained at 72C, and tumbled for 16 hours. ~ 95 percent yield of copolymer was obtained as an aqueous emulsion containing about 30 percent solids.

E~AMPLE 2 .
Preparation of Fluorochemical Copolymer-treated Paperboard A 390 gram mixture of bleached sulfate wood pulp containing equal parts of "Alberta HiBrite" softwood pulp and "Marathon" hardwood pulp was placed in a 0.~8 kg "Voith" laboratory bea-ter apparatus with 23 liters of water. The resultiny mixture was refined for 80 minutes to yield a pulp having a Canadian Standard Freeness of 450 to 500, as measured according to TAPPI Standard No.
T227-05-S~. The refined wood pulp suspension was then diluted wi-th an e~ual volume of water to form a suspension containing about 0.8 percent by weight solids. The diluted suspension was stirred with an electric mixer, and 1250 ml of the stirred mixture (containing about 10 g of refined fiber) was removed and placed in a 2 liter ~raduated cylinder. A 0.15 g portion of cationic polymeric retention aid ("~etz 1275", commercially available from ~etz Laboratories Inc.) was mixed with the contents of the graduated cylinder. Next, 0.12 g (0.04 g on a solids basis) of the copolymer of Example 1 was added to the ~raduated cylinder, followed by mixing. The resulting fiber suspension was E~oured into a 30.5 cm x 30.5 cm paper handsheet mold having an 80 mesh stainless steel screen (commercially available from Williams ~pparatus Co.) and containing 10 liters of water. The perforated stirrer was moved up and down 3 times to mix the fiber suspension and water, and the mold then drained. The screen, wet hand-sheet and two paper blotters were pressed usin~ a hand roller~ rrhe screen was removed from the sheet, two paper -17- ~2~

blotters were placed on the wire side of the sheet, and the resulting assembly was squee~ed in a hydraulic press at a pressure oE 6.9 MPa. The pressed handsheet was dryed in a

4~ cm x 51 cm sheet dryer (commercially available from Willlams Apparatus Co.) that had been set at an initial temperature of 150C. After insertion of the pressed hanclshee-t, the temperature of the metal dryer plate decreased to about 100~C. The handsheet was removed after the plate temperature recovered to 120C. A similarly prepared and dried handsheet was cut in half~ One half was ayed by heating in a forced air oven (commercially avail-able from Despatch Oven Co.) at 120C for 15 minutes, and the other half was aged by equilibrating at 22C, 50% R.~.
for 5 days. Next, each of the above-described handsheet samples was cut into 12.7 cm x 12.7 cm s~uares. The square sheets were folded into square trays each having 2.5 cm deep sidewalls and a 7.7 cm x 7.7 cm base.
The treated handsheet samples were evaluated for oil repellency by~ filling two of each of the trays with corn oil ("Mazola", commercially available from Best Foods division of CPC International, Inc.) and placing the filled trays (and enough other filled test trays to bring the total number o~ filled test trays to 20) on a single oven rack in a preheated 204C electric oven for 30 minutes.
Such temperatures and times exceed those generally used to evaluate existing fluorochemical oligomer-treated paperboard.
The heated trays were removed, emptiedl and inspected on the outer surfaces of the sides, base, and corner creases for staining. The oil repellency of the treated handsheets was evaluated visually according to the following scale:
0 = staining after tray filled and before tray heated 1 = very heavy staining (of sides, bottom and creases) 2 = heavy staining (mainly of bottom and creases) 3 = moderate staining (mainly of creases) 4 = staining of creases only

5 = no staining.
~ t~QC~ k The treated handsheet was evaluatecl for water repellency by filliny two each of the treated trays with 1 percent aqueous sodium chloride solution and placing the trays (and enough other filled test trays to bring the total number of filled test trays to 20) in a 204C
electric oven for 30 minutes. The trays were removed and emptied, and evaluated for staining using the above criteria.
Set out below in Table II are the oil and water repellency ratings obtained for each of the above-described handsheet samples~

TABLE II

Repellency rating Corn Aqueous Handsheet sample oil NaCl not aged 4O5 aged at 120C for 15 min. 4.5 4.5 aged at 22C, 50~ R.H. for 5 days 4.5 4.5 The copolymer of Example 1 was used to prepare additional handsheets with dimensions of 30.5 cm x 30.5 cm x 0.53 mm, containing about 30 g refined treated fiber.
The handsheets were aged in a forced air oven at 120C for 30 minutes, and formed into trays as described above.
Various commercial frozen food products containing oily or aqueous fluids were placed in the trays. Two foods were thawed, heated, placed in the trays while hot, and refrozen.
The food-filled trays were heated in a conventional oven or in a microwave oven, and the trays then evaluated for staining using the above-described criteria. Set out below in Table III are the food type, tray-filling method, cooking conditions, and repellency ratings obtained.

TABLE III

Tray filling Cookiny conditions Repellency Food methodl Gven2 'remp. Time rating ~ . . ~
Chili3 H C200~C 30 min. 5 Chili3 ~ M __8 7.25 min. 5 Beef stew4 H C200C 30 min. 5 Beef stew4 H M --9 9.25 min. 5 Fish5 and French Fries6 F C 200C 30 min. 5 Fish5 and French Eries6 F M --~ 7.25 min. 5 Pancakes and sausages7 F C 200C 30 min. 5 Pancakes and sausages7 F M __10 5 min. 5 1 "H" - thawed, heated, placed in tray while hot, and re--rozen.
"F" = placed in tray while frozer~
2 "C" = conven~ional oven ("Kenmor~ ~model 911.9337910 electric range, commercially available from Sears, Roebuck and Co.).
"M" = microwave oven ~"Kenmore" model 747.9957910 1.5 Kw mi rowave ~en; commercially available fran Sears, Roebuck and Co.).
3 "Hormel" chili and beans, cammercially available fram ~eo. A.
~lonnel & Co. ~
4 "Banquet Buffet Supper", ccmnercially avallable fram Ban~[uet Food Corp.
5 "Gorton's of Gloucester", cammercially available fram General Mills, ~nc.

6 "Ore-IdaA~, cammercially available from Ore-Ida Foods, Inc.

7 "Swans~", commercially available from Campbell Soup Co.

8 5 min. at "3" (Derost) setting, and 2.25 min. at "10" (High) setting.

9 5 min. at "3" setting, and 4.25 min. at "10l' setting.

10 5 min. at "10" setting.

This example shows that the fluorochemical copolymers of this invention provide excellent oil and water repellency on paperboard, under both laboratory and actual food cooking conditions.
trc~de ~n CQ rk -20~ 9~

E~AMPLES 3 to 32 Using the methods of Examples 1 and 2, several fluorochemical copolymers were prepared, exhausted on-to cellulose fiber, made into paperboard, and evaluated. Some of the treated paperboard samples were aged at 22~C and 50 percent relative humidity for several days, or at 120~C in a forced air oven for several minutes. Set out below in Table IV are -the copolymer charging ingredients and amount in grams of each ingredient for each example. Set out below in Table V are the percent loading of copolymer sollds on fiber, amount and type of retention aid, aging time, and oil and water repellency ratings for paperboard treated with the copolymers of Table IV.
These examples show the use of various types and amounts of the monomers of Formulae I, II, III and IV to prepare fluorochemical copolymers of this invention Also, the use of vin~vlidene chloride and various ernulsifying agents is shown in these examples.
Example 8 is a rerun of Exa~ples 1 and 2. When paperboard treated with the copolymer of Example 8 was aged at 22C and 50~ R.H. for 2 hours prior to evaluation, a water repellency rating of 1 was obtained. When paperboard treated with the copolymer of Example 8 was aged at 22~C
and 50~ R.~. for 5 days prior to evaluation, a water repellency rating of 4 was obtained, indicating that aging 25 of the treated paperboard provided irnproved water repellency.

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Fluorochemical copolymers were prepared in a series of five runs labeled "A", "B", "C", "D", and "E".
Set out below in Table VI are ingredient numbers~ copolymer 5 charging ingredients, and amounts of each ingredient (in grams) used in each of Runs A-E:

TABLE VI

Ingre-dient Run, amount in grams 10No. Co~olymer charging ingredient A C D E
C8F17SO2N~CH3~c2E~4ccOGH=cH2 277 277 218 327 257 2 C2H5Cc2H40c()cH=~H2 70 5 70-5 55 83 65 o 3 CH2OE]CH2ccOc~c~3)=cH2 22.5 22.5 18 27 21 15 4 CE12=C(CH3)aO0C2H4N~(CH3)3 Cl 16 16 12.4 18.6 14.6 N2[C(CH3)2C(NH2)=~ Hcl]2 1.3 1.3 1~5 1.5 0.12 6 ClgH37N~(cH3)(c2H4o)xH 12 12 9.3 14 11 ~C2H4O)yH Cl-, x+y=15 7 n-C8H17SH 1.1 1.1 0.86 1.32 1.03 20 8 water 764 764 689 1009 794 9 acetone 89.5 89.5 In Run A, ingredient nosO 1 to 4, 6 to 8 and 724 g water were prehomogenized using two passes through a "Manton-Gaulin" Homogenizer operated at 70~C and 17.2 MPa.
25 The resulting prehomoyenized mixture was added to a one liter, three-neck round bottom reaction flask equipped with a condenser, the~mometer, and mechanical stirrer.
Ingredient no. 5 was added to 40 g water and the resulting mixture was added to the reaction flask. The contents of 30 the flas~s were stirred for four hours at 80C, cooled, and filtered to remove a small amount of solid by-produc t. The filtrate was labelled copolymer emulsion "A"
In Run B, the procedure of Run A was repea-ted but the mixture of ingredient no. 5 in water was placed in the -27- ~2~

reaction flask first, the reaction flask contents were stirred at 80C, and the prehomogenized rnixture of the remaining ingredients was held at 70~ and added gradually to the reaction flask over a 50 ~ninute period. The reaction mixture was stirred for four hours at 80C, cooled and filtered as in Run A, yielding copolymer emulsion "~".
In Run C, the procedure of Run B was followed but a 613 g portion of water was used irl the prehomogenized mixture, ingredient no. 4 was excluded therefrom and the homogenizer was operated at 51.7 MPa. Ingredient no. 4 was disso]ved in 36 g water and added to the reaction Elask as a separate addition stream during the addition of the prehomoyenized mixture The collected filtrate was labelled copolymer emulsion "C".
r. . _ In Run ~D~, ingredients nos. l to 3, 6 to 8, and ~` 920 g water were heated to 70C, ingredient no. ~ was added to the heated mixture, and the resulting mixture was pre-homogenized using one pass through the homogenizer at 70C
and 51.7 MPa. Ingredient no. 5 and 89 g water were added to the reaction ~lask and heated to 80Co Several hundred grams of the prehomogenized mixture were drawn off from the homogenizer and discarded. A 93~ g portion of the pre homogenized mixture was drawn off from the homogenizer and added to the reaction flask over a 15 minute period, and 25 the remainder of the prehomogenized mixture was discarded.
The reaction mixture was stirred for four hours at 80C, cooled, and filtered as in Runs A-C, yielding copolymer emulsion "D".
In Run E, the procedure of Run D was followed but 30 a 724 g portion of water was added to the homogenizer, ingredient noO 5 and 70 g water were added to the reaction flask, and all of the preho~logenized mixture was added to the reaction flask. The collected filtrate was labelled copolylner emulsion "E", and was found to be more stable (as 35 measured using a centrifuge) than copolymer emulsion "D".
The copolymer emulsions of Runs A-E were exhausted onto cellulose fiber, made into paperboard, and -28- ~2~9~
evaluated as in Example 2. Set out below in Table VII are the percent loading of copolymer solids on fiber, amount and type of retention aid, aging time, and oil and water repellency ratings (average of two samples) for paperboard treated with the copolymers of Runs A-E. Kit ratings for oil repellency were determined in accordance with TAPPI
Useful Method 557.

T~BLE VII

Run A B C D E
% Copolymer on fiber 0.5 0.50.45 0.45 0.45 Retention aid, % on fiber Polymeric cationic aliphaticamide(a) 1.5 1.5 1.5 1.5 1.5 Agi~
Days at 22C, 50% R.H.

Repellency rating Corn oil 4O3 5 4.8 5 5 Aqueous NaCl 2.5 3 5 4~8 4.8 Kit 6.5 6.5 6 6.2 6.5 (a) "Betz 1275"

To evaluate the utility oE a fluorochemical copolymer of this invention as a textile treatment, a loosely knitted fabric of carrierless polyester staple carpet yarn (12 denier per filament) was treated Witil a padding bath containing 0.68 wt. % of the fluorochemical copolymer of Example 33 Run C, to provide 0.21% solids on fiber. The treated fabric was dried for 15 minutes at 160C, disperse dyed using a "Launder-Ometer" laboratory dyeing machine (Model LEF, commercially available from the ~2~

A-tlas Electric Devices Company), and dried Eor 10 minutes at ]30C The treated fabric was found to have an oil repellency rating of 4 as measured using AATCC Standard Test 118-1978 (modified by waiting 10 seconds instead of 30 seconds before measuring oil repellency). The aqueous stain repellency of the treated fabric was measured using a water/isopropyl alcohol test. In such testl aqueous stain repellency is expressed in terms of the "WAT~R/IPA" rating of the trea~ed fabric. Treated fabrics which are pene-trated by or resistant only to a 100% water/ 0% isopropylalcohol mixture, the least penetrating of the test mixtures, are given a rating of 100/0, whereas treated fabrics resis-tant to a 0% water/100~ isopropyl alcohol mixture, the most penetrating of the test inixtures, are given a rating of 0/100. Other intermediate values are determined by use of other water/isopropyl alcohol rnixtures, in which the per-centage amounts of ~ater and isopropyl alcohol are each multiples o~ 10~ The WArrER/IPA rating corresponds to the most penetrating mixture which does not penetrate or wet the fabric after 10 seconds contact. In general, a WATER/IPA rating of <50/>50 is desirable. The treated fabric of this example had a WATER/IPA rating of 40/60.
The resistance of the treated fabric to loss of performance during dyeing was evaluated by measuring the fluorine content of the treated fabric before and after dyeing. The treated fabric had 605 ppm fluorine ~efore dyeing and 601 ppm fluorine after dyeing, indicating that nearly 100 percent of the fluorochemical copolymer was retained on the fabric after dyeing.

Using the methods ~f Examples 1 and 2, several fluorochemical copolymers were prepared, exhausted onto cellulose fiber~ made into paperboard, and evaluated. Some of the treated paperboard samples were aged at 22C and 50 percent relative humidity for several days, or at 120C in a forced air oven for several minutes. Set out below in Table VIII are the copolymer charging ingredients and amount in grams of each ingredient for each comparative example. Set out below in Table IX are the percent loading of copolymer solids on fiber, amount and type of retention aid, aging time, and oil and water repellency ratings for paperboard treated with the copolymers of Table VIII.
These Comparative Examples SilOW that paperboard treated with copolymers derived from fluoroaliphatic methacrylates have poorer oil and/or water repellency than paperboard treated with copolymers derived from fluoro-aliphatic acrylates (compare, e.g., Comparative Example 1 with Examples 11 and 12, and Comparative Example 2 with ~ Example 19). When n is zero in the monomer of Formula II, use of too large an Rl radical provided poor wa~e~
repellency on treated paperboard (see Comparative Examples 3 and 4). Use of hydroxyl-containing monomers resulted in formation of copolymers which provided poor water repellency (and sometimes poor oil repellency) on treated paperboard (see Comparative Examples S and 6). When the monomer of Formula III was omitted, the resulting copolymer provided poor water repellency on treated paperboard (see Comparative Example 7). If a copolymer was derived from only 1 weight percent of the monomer of Formula III~
paperboard treated therewith had poor water repellency (see Comparative Example 8). When a copolymer was prepared wi-th-out the monomer of Formula IV, paperboard treated therewith had poor oil repellency (see Comparative Example 9)~ I~ no chain transfer agent was employed, or if a large excess of chai.n transfer agent was employed, the resulting copolymer had too high or too low a molecular weight, respectively, and paperboard treated therewith had no oil or water repellency (see Comparative Examples 10 and 11).

-31- ~2~9~

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Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention and the latter should not be restri.cted to that set for-th herein for illustrative p~rposes.

Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Fluorochemical copolymers useful for imparting oil and water repellency under food cooking conditions to cellulosic materials, or oil and water repellency to textile fibers, said copolymers comprising (by weight):
(a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula:

(Rf)pQOCOCH=CH2 wherein Rf is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2;
(b) 1 to 30% of polymer chain repeat units derived from alkyl or alkoxyalkyl acrylate or methacrylate monomer of the formula:

R1O(R2O)n[C(O)CH2O]mCOCR3=CH2 wherein R1 is a C1-20 alkyl or cycloalkyl group, R2 is a C1-6 alkylene group, each R2 group can be the same as or different from other R2 groups, n is zero to 10 with the proviso that when n is zero R1 is a C1-16 alkyl or cycloalkyl group, m is zero or 1, and R3 is H or methyl;
(c) 2 to 15% of polymer chain repeat units derived from monomer of the formula:
wherein R4 is H or methyl;
(d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula:

CH2=C(R5)ZY+X-wherein R5 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymeriza-tion, Y+ is a monovalent cationogenic group, and X- is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride;
with the proviso that the weight percent of carbon-bonded fluorine in said copolymers is at least 15%.

2. Fluorochemical copolymers according to Claim 1, wherein Q is -CH2-, -C2H4-, or -SO2N(R6)C2H4-, where R6 is H or a C1-4 alkyl radical.

3. Fluorochemical copolymers according to Claim 1, wherein n is zero.

4. Fluorochemical copolymers according to Claim 1, wherein n is 1 and m is zero.

5. Fluorochemical copolymers according to Claim 1, wherein R1 is a C1-4 alkyl radical and R2 is a C1-4 alkylene radical.

6. Fluorochemical copolymers according to Claim 1, wherein R1 is CH3CH2-, R2 is -C2H4-, n is 1, m is zero, and R3 is H.

7. Fluorochemical copolymers, comprising (by weight):
(a) 65 to 75% of polymer chain repeat units derived from C8F17SO2N(CH3)C2H4OCOCH=CH2;
(b) 10 to 20% of polymer chain repeat units derived from CH3CH2OC2H4OCOCH=CH2;
(c) 3 to 10% of polymer chain repeat units derived from ;
(d) 2 to 4% of polymer chain repeat units derived from CH2=C(CH3)COOC2H4N+(CH3)3 Cl-; and (e) 0.1 to 0.8% of chain transfer agent.

8. Ovenable paperboard, having incorporated thereon fluorochemical copolymer according to Claim 1.

9. Ovenable paperboard, having incorporated thereon fluorochemical copolymer according to Claim 6.

10. Ovenable paperboard, having incorporated thereon fluorochemical copolymer according to Claim 7.

11. Textile fibers, having incorporated thereon fluorochemical copolymer according to Claim 1.

12. Textile fibers, having incorporated thereon fluorochemical copolymer according to Claim 6.

13. A process for imparting high temperature oil and water repellency and food stain resistance to cellulosic material, comprising the step of applying to said material at least one fluorochemical copolymer com-prising (by weight):
(a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula:

(Rf)pQOCOCH=CH2 wherein Rf is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2;
(b) 1 to 30% of polymer chain repeat units derived from alkyl or alkoxyalkyl acrylate or methacrylate monomer of the formula:

R1O(R2O)n[C(O)CH2O]mCOCR3=CH2 wherein R1 is a C1-20 alkyl or cycloalkyl group, R2 is a C1-6 alkylene group, each R2 can be the same as or different from other R2 groups, n is zero to 10 with the proviso that when n is zero R1 is a C1-16 alkyl or cycloalkyl group, m is zero or 1, and R3 is H or methyl;
(c) 2 to 15% of polymer chain repeat units derived from monomer of the formula:
wherein R4 is H or methyl;
(d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula:

CH2=C(R5)ZY+X-wherein R5 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymeriza-tion, Y+ is a monovalent cationogenic group, and X- is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride;
with the proviso that the weight percent of carbon-bonded fluorine in said copolymer is at least 15%.

14. A process according to Claim 13, wherein is CH3CH2-, R2 is -C2H4-, n is 1, m is zero, and R3 is H.

15. A process according to Claim 13, wherein said fluorochemical copolymer comprises (by weight):
(a) 65 to 75% of polymer chain repeat units derived from C8F17SO2N(CH3)C2H4OCOCH=CH2;
(b) 10 to 20% of polymer chain repeat units derived from CH3CH2OC2H4OCOCH=CH2;
(c) 3 to 10% of polymer chain repeat units derived from ;
(d) 2 to 4% of polymer chain repeat units derived from CH2=C(CH3)COOC2H4N+(CH3)3 Cl-; and (e) 0.1 to 0.8% of chain transfer agent.

16. A process for imparting oil and water repellency to textile fibers, comprising the step of applying to said fibers at least one fluorochemical copolymer comprising (by weight):
(a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula:
(Rf)pQOCOCH=CH2 wherein Rf is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2;
(b) 1 to 30% of polymer chain repeat units derived from alkyl or alkoxyalkyl acrylate or methacrylate monomer of the formula:

R1O(R2O)n[C(O)CH2O]mCOCR3=CH2 wherein R1 is a C1-20 alkyl or cycloalkyl group, R2 is a C1-6 alkylene group, each R2 group can be the same as or different from other R2 groups, n is zero to 10 with the proviso that when n is zero R1 is a C1-16 alkyl or cycloalkyl group, m is zero or 1, and R3 is H or methyl;
(c) 2 to 15% of polymer chain repeat units derived from monomer of the formula:
wherein R4 is H or methyl;
(d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula:

CH2=C(R5)ZY+X-wherein R5 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymeriza-tion, Y+ is a monovalent cationogenic group, and X- is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride;
with the proviso that the weight percent of carbon-bonded fluorine in said copolymers is at least 15%.

17. A process according to Claim 16, wherein said fibers comprise polyester carpet fibers.