Aziridinyl polyolefins and method of preparing same
United States Patent 1 1 m1 3,876,593  
 Tesoro Apr. 8, 1975 AZIRIDINYL POLYOLEFINS AND METHOD [56] References Cited 0F PREPARING SAME UNITED STATES PATENTS [75] Inventor: Giuliana C. Tesoro, Dobbs Ferry, 2,852,497 9/1958 Thompson 260/793 R N.Y. 3.001.965 9/l9 6l Kalil 260/285 3.230.029 l/ 19.66 Cappuccio 8/55 [73] Assrgnee: J. P. Stevens &amp; Co., Inc., New York,  
  Primary E.\&#39;anii|ier-Christoper A. Henderson [22] Filed: Feb. 7, 1972 Attorney, Agent, or FirmMichael T. Frimer; Charles St 211 Appl. No.: 224,355  
  Related U.S. Application Data [57] ABSTRACT Continuation of April 30, 1965. Novel polymers are derived from chlorosulfonated abandmledpolyethylene by replacing chlorine atoms in the chlorosulfonyl groups with aziridinyl radicals. These poly- U-S- mers can be used to improve the properties of wool 8/l28.5; 260/80; 260/8072; 260/8 and cellulosic te-xtile materials. Additionally, the poly- CL 7/123 Cosf 27/08; Cosf 15/00 mers can be crosslinked to form a product useful as a [58] Field of Search 260/793 R, 2 EN, 239 E; bindcm AZIRIDINYL POLYOLEFINS AND METHOD OF PREPARING SAME This is a continuation of application Ser. No. 452,385, filed Apr. 30, 1965 and now abandoned.  
  This invention relates to novel polyolefins as well as to methods of preparing said polyolefins. More particularly, this invention relates to the preparation of polyolefins containing reactive aziridinyl groups.  
  It has been proposed to modify various textile materials with polyolefins in order to impart to such materials properties of dimensional stability, tear strength, abrasion resistance, and the like. However. cellulosic textiles, when treated with polyolefins, do not maintain the desired degree of tear strength and abrasion resistance upon continued laundering. Also, proteinaceous materials like wool often undergo modification only at the cost of fiber bonding and impairment of hand.  
  It is an object of this invention to provide novel polyolefins which can be employed in the modification of textile materials and polymeric materials containing active hydrogen atoms.  
  It is another object of this invention to provide a process for the synthesis of the aforementioned polyolefins.  
  A further object of this invention is to provide a process for shrinkproofing keratin fibers and particularly wool.  
  A still further object of this invention is to provide a process for enhancing the strength characteristics of cellulosic textiles.  
  Other objects and the advantages of this invention will be apparent from the description that follows.  
  ln accordance with this invention there are prepared polymeric derivatives of chlorosulfonated polyethylene wherein chlorine atoms in the SO Cl groups of chlorosulfonated polyethylene are replaced with aziridine radicals selected from the group consisting of C N l CH2 --N\ l CH2 CH3 and  The above polymeric derivatives can be prepared by reacting chlorosulfonated polyethylene with either ethylene imine or propylene imine in the presence of an acid acceptor. Suitable acid acceptors include inorganic bases such as alkali or alkaline earth carbonates and organic bases of comparable strength free of active hydrogen atoms, e.g., tertiary amines such as triethylamine.  
  The reaction is conveniently carried out in an inert solvent such as chlorinated solvents (e.g., carbon tetrachloride, perchloroethylene, and the like), hydrocarbon solvents (e.g., toluene, xylene and the like), and  
  l C SO Cl cnl l /CH2 HN l where z represents the number of repeating units in the polymer molecule.  
  The reaction is generally carried out at temperatures of from about zero degrees to about 50C. Ambient temperatures in many instances can be used conveniently. The reaction times required for completion of the reaction vary considerably, depending on the structure and concentration of the starting materials, on the solvent and on the acid acceptor.  
  The aziridinyl modified polyolefins may also undergo self-crosslinking&#34; by heating for from about 2 to 20 minutes at temperatures greater than C, and preferably from about C. to about C.  
  Under suitable conditions, the aziridinyl polyolefins, or their precursors, of the present invention may be admixed and reacted with compounds containing active hydrogen to form new products.  
  The aziridinyl modified polyolefins of this invention are of particular-utility in improving the dimensional stability of keratin fibers (especially wool) and in enhancing the strength characteristics of cellulosic textiles. Moreover, the aforementioned improvements in textile materials are accomplished without detrimentally affectingthe aesthetic properties of the materials, The polyolefins are&#39;stable in the presence of moisture and thus can be formulated as aqueous emulsions or as organic solvent solutions and subsequently applied to the desired textile material.  
  When applied to textiles comprising wool, the modified polyolefins may be employed in amounts as low as about 2%, by weight, as based on the weight of the wool. Although the quantity of polyolefin used is surprisingly small, essentially complete dimensional stability of the wool fabric is possible. The application of the modified polyolefins may be carried out on conventional equipment and other additives, e.g., stain repellents, may be combined with the polyolefins in order to obtain several functional properties in a single process.  
  When applied to cellulosic textiles, the modified polyolefins not only increase the tear strength and abrasion resistance thereof, but also improve the hand and appearance of the textiles. In fact, cotton fabrics acquire silk-like drapeability and feel when finished with the polyolefins of this invention. It is particularly advantageous that these enhanced properties are retained through numerous launderings.  
  As was mentioned previously, the reactive polyolefins may also undergo self-crosslinking. They can thus be applied as emulsions or organic solvent solutions to non-woven fibrous assemblies and subsequently cured, in situ, to obtain the bonded product.  
  The aziridinyl polyolefins of this invention are effective whether or not the material to be treated contains active hydrogen atoms. In the absence of active hydrogen atoms crosslinking of the aziridinyl polyolefins&#39;is believed to occur through polymerization of the aziridinyl groups. In the presence of active hydrogen atoms, the aziridinyl groups are believed to react with such atoms, thereby forming chemical covalent bonds. It is also within the contemplation of this invention that the aziridinyl polyolefins may be used to graft polyolefin chains on any polymer containing active hydrogen atoms.  
  In the examples which follow, all parts given are by weight unless otherwise indicated. The test results shown in the examples were obtained according to the following methods.  
 Stiffness Cantilever procedure ASTM-D-l388-55T Tear Strength ASTM-Dl424-63 Tensile Strength Ravel Strip Method ASTM-D1682-59T ASTM-D-l175-61T (Stoll Flex Abrader. V2 lb. head. 2 lbs. toggle) Wool samples laundered in automatic house-type agitator washing machine at 105F. for the full cycle. except minutes suds time (household detergent). 5 1h. load. Samples were dried flat on horizontal screen. flat-bed pressed for 5 seconds (no steam). ASTM-E97-55. Photovolt 610 and Search Unit 6104. using the green tristumulus filter. (Cotton): Samples laundered in automatic home-type agitator washing machine at 140F. for the full cycle (household detergent). 5 lb. load. Samples flat-bed pressed. Minnesota Mining Bulletin on Fluorochemicals. Appendix A. Pages 1-2.  
 Flex Abrasion Shrinkage Reflectance Laundering Oil Repellency Example 1 PREPARATION OF POLYETHYLENE SULFONYL ETHYLENE IMINE To athree-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 3.1 parts potassium carbonate and 1.5 parts ethylene imine dissolved in 100.0 parts toluene. The mixture was then stirred and kept at l520C. and into the cooled mixture 50 parts of Hypalon (a chlorosulfonyl polyethylene rubber, %S 1.4%, %CI 29.0%, made&#39; by E. I. du Pont according to US. Pat. No. 3,119,830) dissolved in 300.0 parts toluene were added dropwise. The addition was completed in 1 hour. The mixture was then stirred for an additional 2 hours at to C. The inorganic materials were then filtered off and the homogeneous solution was placed under vacuum to drive off residual unreacted ethylene imine. The percent solid content of the viscous clear solution, determined from the weight difference of a sample heated to dryness at 130C., was found to be 12.0%. A heat-cured sample of the residual solid, after extraction with toluene, acetone and water and drying was found to have 0.53% N, which corresponded to an 86% yield in the amidation of the chlorosulfonyl group in the Hypalon 20.  
 EXAMPLE 2 PREPARATION OF POLYETHYLENE SULFONYL ETHYLENE IMINE To a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 4.3 parts potassium carbonate and 1.5 parts ethylene imine dissolved in 100.0 parts toluene. The mixture was stirred and cooled to l520C. To the mixture 100.0 parts Hypalon 30 (a chlorosulfonyl polyethylene rubber %S 1.0%, %CI 4.2% made by E. I. du Pont, according to US. Pat. No. 3,119,830) dissolved in 400.0 parts toluene were added dropwise. The addition was completed in 1 hour. After the addition, the mixture was stirred for 2 hours at l520C. and another 2 hours at 25-30C. The inorganic materials precipitated were separated by filtration, and unreacted ethylene imine was stripped off under vacuum at room temperature. The solid content of the homogeneous viscous solution was 13.0% determined in the same manner as in Example 1. A cured sample after extraction with toluene, acetone and water and drying was found to contain 0.57% N which corresponds to a 100% yield in the amidation of the chlorosulfonyl groups in the I-lypalon 30.  
 EXAMPLE 3 PREPARATION OF POLYETHYLENE SULFONYL PROPYLENE IMINE To a three-necked flask equipped with a stirrer. a reflux condenser, a thermometer and a dropping funnel were charged 6.] parts potassium carbonate and 2.8 parts propylene imine dissolved in 100.0 parts toluene. To the stirred and cooled mixture (l520C.) 100.0 parts Hypalon 20 dissolved in 400 parts toluene were added dropwise over a period of 1 hour. After the addition was completed, the mixture was stirred for 2 hours at 15C. and another 2 hours at 25-30C. The inorganic materials precipitated were separated and unreacted propylene imine was stripped off under vacuum at room temperature. The solid content of the homogeneous and viscous solution determined as described in Example 1 was found to be 13.0%.  
 EXAMPLE 4 PREPARATION OF POLYETHYLENE PHOSPl-IONYL ETHYLENE IMINE A mixture of 50.0 parts of polyethylene (av. mol. wt. 2,000) and 500.0 parts phosphorus trichloride were heated at C. in a four-necked flask equipped with a mercury-sealed stirrer, a thermometer, a dryice/ethanol condenser and a gas capillary tube. Dry oxygen was slowly bubbled through the gas tube beneath the surface of the reaction mixture. The exit gas was passed through a trap immersed in a dry ice-acetone mixture to condense the entrained phosphorus trichloride and phosphorus oxychloride, and finally into a trap containing 250.0 parts of distilled water to absorb the hydrogen chloride evolved. The absorbed acid was titrated periodically with standard base over a period of 6 hours to determine the rate of reaction. The rate of phosphorylation determined from the evolved hydrogen chloride was approximately 0.1 milliequivalent of phosphorus introduced per hour per gram of polyethylene. After 6 hours of reaction under these conditions, the oxygen flow was stopped and the PCl and POCl were distilled from the reaction mixture at 5060C. The recovered product was a light brown rubberlike solid.  
  A solution of 50.0 parts of the phosphorylated polyethylene dissolved in 800.0 parts of toluene was then charged into a three-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. The solution was kept at 5l0C., and into the cooled solution 7.1 parts of ethylene imine and 16.7 parts of triethylamine dissolved in 200.0 parts of tolu ene were added dropwise. The addition was completed in 1 hour and the solution was stirred for another 3 hours at 2530C. The unreacted ethylene imine was then distilled off from the mixture under vacuum at room temperature. The solid content of the homogeneous solution, determined by the method used in Example l, was found to be 4.0%.  
 EXAMPLE 5 GELATION OF POLYETHYLENE SULFONYL ETHYLENE [MINE The polyethylene sulfonyl imine prepared according to the procedure of Example 1 was cured by selfcrosslinking when exposed to heat. The rate of gelation was found to increase with the time of heating.  
  into three weighing dishes were placed 20.0 parts of the 12.0% toluene solution of the product of Example 1. The dishes with their contents were heated at 130C. in an oven for a period of minutes, minutes and minutes, respectively. At the end of the curing time, the contents of the dish were extracted well with toluene, acetone and water and, finally dried to a constant weight. The weight difference before and after curing and subsequent extraction and drying was taken to measure the percent yield in the gelation of the polyethylene sulfonyl ethylene imine.  
  The polyethylene sulfonyl ethylene imine, when gelled within a fibrous substrate, acted as a binder therefor.  
 EXAMPLE 6 Example 5 was repeated using the product of Example 2 in place of the product of Example 1. The following results were obtained:  
 Curing Time (Mins.) Percent Yield of Sample at 130C. Crosslinked Polymer The gelled product serves as a binder for non-woven substrates.  
 EXAMPLE 7 Example 5 was repeated but the product of Example 3 was used in place of the product of Example 1. The following results were obtained:  
 Curing Time (Mins.) Percent Yield of Sample at 130C. Crosslinked Polymer The gelled product serves as a binder for non-woven substrates.  
 EXAMPLE 8 in accordance with this procedure were as follows:  
  STIFF- FLEX REFLEC- /r Rea- XSHRINKAGE NESS ABRA. TANCE gent Sam- Applied /(Wt. 5L 10L mg/cm&#34; cycles ple (OWF) Gain W W F W W A 4.3 3.1 0.5 1.5 0.5 1.5 185 750 B 3.1 2.2 1.5 2.0 2.0 2.0 1 52 725 60 C 2.1 1.7 2.5 2.5 3.0 3.5 130 650 60 D 1.1 g 4.0 4.5 8.0 7.5 575 60 Untreated Control 13.5 1.5 24.0 20.5 83 v 600 61 L Launderings as specified OWF On Weight of Fabric WLGain Weight increase due to treatment (after washing) Curing Time (Mina) Percent Yield of Sample at C. Crosslinked Polymer &#34;/(SHRlNKAGE &#39;71 Reagent Curing Time after 51. Sample Applied (OWF) in Minutes W F A 4.0 14.5 12.5 4.0 12.5 10.0 Untreated Control 16.5 14.5  
  From this control experiment, it is apparent that the conversion of the Hypalon to the aziridinyl derivative is essential for obtaining the desired shrinkproofing effect on wool.  
 EXAMPLE 9 Samples ofa 100% woolen fabric in the rcady-to-dye state were treated with the product of Example 1, from an aqueous emulsion.  
  The emulsion was prepared by mixing a 12% toluene solution of the product of Example 1, with an equal amount of a 12.8% aqueous solution of potassium oleate using a high speed stirrer. The emulsion was homogenized in a colloid mill and diluted to the desired concentration with a 6.4% aqueous potassium oleate solution.  
  The fabric samples were treated with the emulsion using a laboratory padder setting the rolls at such a Samples of 100% woolen fabric in the ready-to-dye state were treated with Hypalon 20 from toluene solution using a laboratory padder at such a pressure to give 120% wet pickup. The fabric samples so treated were dried at 60C. on frames. The dried samples were then treated with an aqueous solution of aminoethyl sulfuric acid (AES) and K CO using a laboratory padder to give 1 13-1 19% wet pickup. The fabric samples so treated were again framed to the original dimensions and dried at 60C., then cured at 150C. for 15 minutes in a forced-draft oven. The cured fabric samples were rinsed in toluene, dioxane and finally in water.  
 The samples were then framed and dried.  
 The following results were obtained:  
 REAGENTS APPLIED samples so treated were framed and dried at 60C., then cured for 15 minutes at 150C. in a forced draft oven. The cured fabric samples were rinsed in toluene, dioxane and finally in water. The samples were then framed to the original dimensions and dried. Test results were as follows:  
 (OWF) (OWF) (OWF) &#34;/(Weight AFTER 5L Sample (1st padding) (2nd padding) Increase W F A 4.6 0.25 0.24 3.4 3.5 6.0 B 2.4 0.12 0.12 3.0 4.0 5.5 Untreated Control 19.0 1 1.5  
 &#39; ressure as to ive a 96l03% wet icku The fabric g P P EXAMPLE 13 Example 8 was repeated using the product of Example 4 in place of the product of Example 1. The samples were cured at 160C. for the time specified below, and the following results were obtained:  
  /rReagent /(SHR1NKAGF. AFTER STIFFNESS FLEX Applied 51. 101. mg/cm ABRASION Sample (OWF) W F W F W Cycles-W A 4.1 3.0 2.5 3.5 2.5 132 700 B 3.0 3.0 3.5 3.5 3.5 107 700 C 2.0 5.0 5.5 7.5 6.5 89 650 D 1.0 7.0 4.5 10.0 6.5 )5 550 Untreated Control 18.0 14.5 20.5 17.5 86 575 7rRea- Curing Time 71SHRINKAGE gent EXAMPLE 10 Applied in 51.  
 - 1 OWF M&#39; 1 w P Example 8 was repeated but the product of Example e 3 was used in place of the product of Example 1 and the A 4.8 5 6.5 5.5 curing time at 150C. was varied. The following results 2 3&#39;7 2 were obtained: D 2.4 15 7.5 81%) Untreated Control 16.5 15.0  
  &#39;71 Reagent Curing &#39;71SHR1NKAGE STIFFNESS FLEX REFLEC- Applied Time in AFI&#39;ER 51. mg/cm&#34; ABRASION TANCE Sample (OWF) Minutes W F W Cycles-W A 4.1 5 1.5 3.5 202 700 59 B 4.2 15 2.0 2.5 191 650 58 C 2.1 5 4.5 3.5 140 650 58 D 2.0 15 2.0 3.5 140 550 58 Untreated Control 18.0 15.0 92 625 60 EXAMPLE 1 l EXAMPLE 14 Example 8 was repeated but using the product of Example 2 in place of the product of Example 1. The samples were cured at 150C. for the time specified below.  
  Samples of plain-weave cotton fabric (commonly known as X 80 print cloth) were treated with the product of Example 1 from toluene solution using a laboratory padder and setting the rolls at such a pressure as to give 75% wet pickup. The fabric samples so treated were framed to the original dimensions and dried at 60C., then cured at 150C. for 10 minutes in reflux condenser, a thermometer and a dropping funnel were charged 12.0 parts of potassium carbonate and 13.6 parts of 2-aminoethane hydrogen sulfate. Into the mixture kept at l520C. were added slowly 100.0  
 a forced-draft oven. The fabric samples were rinsed in 5 parts Hypalon 2O dissolved in 400.0 parts toluene over toluene and dioxane&#39;and then washed at 6070C.with a period of 1 hour. The mixture was then stirred at an aqueous solution of non-ionic detergent. The saml520C. for 2 hours and then at room temperature ples were framed and dried. Thefollowing results were for another 2 hours- The inorganic base and the excess Obtained: Z-aminoethane hydrogen sulfate precipitate were fil- Tensile Flex Abrasion Stitfness W &#39;/i REZI- Strength C ycles After 101. mg/em&#34; Sample (653m v. we. Orig. w w Orig. After L A 2.0 L0 55 son 71 76 B 1.2 0. 57 s25 71 69 C 0.5 0.8 57 700 71 75 Untreated Control 61 650 130 96 It is pp that the treatment improves the abta&#39; tered off and the percent solid content of the homogesion resistance and softness ofthe cotton fabric without neous and viscous solution was found to be 17.9% appreciable 1055 of tensile Strength determined by the procedure described in Example 1.  
  EXAMPLE 15 b. GELATION OF POTASSIUM SALT OF POLY- ETHYLENE AMINO ETHANE SULFONIC ACID A sample Ofa plam&#39;hleave cotton fabnc (Commonly The toluene solution of the potassium salt of the known as 80 80 Prmt cloth) was treated Wlth polyethylene sulfonyl amino ethane sulfonic acid was aqueous emulsloh of the Product of Example gelled in the same manner as described in Example 5&#39;.  
  The emulsion was P p y mixing 500 of a The following results were obtained: 12% toluene solution of the product of Example 3, with C Time (Min Percent Yield of 60.0 of a non-ionic surface active a ent (Triton t X-IO a product of the Rohm &amp; Haas Ch emical Com- Sample 130 Crosslmked Polymer pany) with high speed stirring. The emulsion was 1 l0 stirred for minutes and nitrogen gas was bubbled 30 i8 331 through it. The emulsion obtained in this manner was diluted water to desired concentration. The gelled product erves as a binder for non-woven The cotton fabric sample&#39;was treated with a dilution Substrates, of this emulsion containing 3% active ingredient, using EXAMPLE 17 a laboratory padder and setting the rolls at such a pressure as to get 80% wet pickup. The sample so treated PREPARATION OF POLYETHYLENE was framed to. the original dimensions and dried in a CARBOXYLETHYLENEIMINE forced-draft oven at 60C., then cured at 150C. for 5 To a threemecked fl k equipped with a stirrer, 3 minutes The Cured Sample was Washed at with thermometer, a reflux condenser and a dropping funnel detergent Solution and The Properties of the 40 were charged 5.0 parts potassium carbonate and 1.5 p compared to those of ah untreated Control parts ethylene imine dissolved in 100.0 parts perchlorowere as follows: ethylene. The mixture was then stirred and kept at Treated Sample Untreated Comm] 25C. and into the mixture 70.0 parts of ZESET TP (a terpolymer of ethylene, methacryloyl chloride and fzwggi&#39; zgyfg OWF $1; vinyl acetate, made by E. l. du Pont) dissolved in ft washing 1330.0 parts perchloroethylene were added dropwise. Te tile Strenglt I I 59 6] The addition was completed in 1 hour, and the mixture 6F 60 59 was then&#39;stirred for an additional 3 hours at 25C. The Tear Strength inorganic materials were then separated and the homo- W 965 8 geneous solution was placed under vacuum to drive off Flex Abrasion residual unreacted ethylene imine. The percent solid ags; W 425 375 content of the clear solution, determined from the m /cm Original 104 187 weight difference of a sample heated to dryness at C., was found to be 5.7%. EXAMPLE l6 a. PREPARATION OF POTASSIUM SALT OF POLYETHYLENE AMINO ETHANE SULFONIC ACID 6 Into athree-necked flask equipped with a stirrer, a  
 EXAMPLE 18 Example 9 was repeated, but 2% Scotchgard FC-208 (fluorochemical resin made by Minnesota Mining and 0 Manufacturing Co., St. Paul, Minnesota) was added to the aqueous emulsion of the product of Example 1.  
 EXAMPLE 19 A sample of 100% woolen fabric in the ready-to-dye state was treated with the product of Example 16 from toluene solution using a laboratory padder at such a pressure as to give I wet pickup. The fabric sample so treated was dried at 60C. on frame. The dried sample was overpadded with 0.25% aqueous potassium carbonate solution using a laboratory padder. The fabric sample so treated was framed again to the original dimensions and dried at 60C., then cured at 150C. for 15 minutes in a forced-draft oven. The cured fabric sample was rinsed in toluene, dioxane and finally in water.  
  Reagent Applied &#39;/(Weight &#34;/1 Shrinkage 5L Sample OWF Increase W F Treated 4.6 8.1 1.5 2.5 Untreated Control 20.0 16.0  
 EXAMPLE Samples of 100% woolen &#39;and of 100% worsted wool fabric were treated with the product of Example 17 from perchloroethylene solution using a laboratory padder and setting the rolls at such a pressure to give 140-19070 wet pickup. The fabric samples so treated were framed and dried at 100C. for 2 minutes in a forced draft oven. The dried fabric samples were rinsed in dioxane and water, then framed to the original dimensions and dried. The test results on sample treated in accordance with this procedure were as follows:  
 APPLICATION OF POLYETHYLENE SULFONYL ETHYLENEIMINE AS A NON-WOVEN BINDER Rayon staple non-woven webs were bonded together into strong and flexible cloth with the polyethylene sulfonyl ethyleneimine prepared in Example 1.  
 Two 4-inch by 4-inch non-woven webs were immersed into two 50.00 c.c. toluene solutions containing 2&#39;7: and 5% polyethylene sulfonyl ethyleneimine, respectively. The residence time was 2 minutes and the coated webs were squeezed between glass rods before they were laid on top a wire cloth. The coated webs were then cured at 130C. for 15 minutes in an oven. The cured webs were strong and flexible. After rinsing the cured webs in toluene and acetone, they were dried in an oven at 95C. for 10 minutes. The dried web samples, together with an uncoated non-woven web, were immersed into boiling &#39;water for 30 minutes. The two webs bonded with the polyethylene sulfonyl ethyleneimine still maintained their strength, flexibility and dimensions, whereas an untreated non-woven web completely disintegrated into a fibrous mass.  
  Any departure from the above description which conforms to the present invention is intended to be included within the scope of the invention as defined by the following claims.  
 What is claimed is:  
  l. A polymer consisting essentially of repeating units of the formula CH CH where .r is approximately 12.  
 &#39; 2. A crosslinked polymer obtained by heating the polymeric derivative of claim 1 at temperatures in the range of 125 to 175C.  
  3. A polymeric derivative of chlorosulfonated polyethylene wherein the modification of said chlorsulfonated polyethylene consists essentially of replacement of 86 to 100% of the chlorosulfonyl chlorine atoms of said chlorosulfonated polyethylene with radicals of the formula UNITED, STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO.- 3,876,593  
  DATED &#39;1 April 8, 1975 lNV ENTOR(S Giuliana C. Tes or&#39;o It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Colunm 9, line 50, in the table under &#34;Treated Sample &#34;Tear Strength W Original&#34; the number should read 1.8  
  Column ll, Example 19, in the table &#34;Treated Sample&#34; under Weight Increase&#34;- should read 3.1  
 Column 11, Example 20, in the table, under &#34;Sample Fabric&#34; after &#34;Treated Woolen&#34; the omitted-line should be inserted as follows: Reading across, under the first column insert Untreated Woolen&#39;-; second column leave space blank Q third column insert a dash; fourth column insert .l5.5  
 fifth column insert 13.5 and in the last column insert Signcd and Scaled this Q Twenty-fourth D3) Of August 1976 [SEAL] I Arrest.  
 Q RUTH. C. MAISON C. MARSHALL DANN I AIR-&#34;mg Off? Commissioner uj&#39;larents and Trademarks