JPH07505450A - Anti-staining agent for polyamide substrates - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Anti-staining agent for polyamide substrates Cross references to related applications The present invention is based on U.S. Patent Application No. 07/626.885, filed December 13, 1990. No. 07/809, filed Dec. 18, 1991, a continuation-in-part application of No. ．． This is a continuation-in-part application of No. 843.

field of invention The present invention relates to stain resistant polymeric compositions.

Background of the invention Polyamide substrates such as nylon carpets and upholstery fabrics can be used for various active substances. susceptible to contamination from food and beverages. Particularly troublesome agents that create contamination are FD & CRed Dye No. 40 commonly found in todrink formulations . Various types of treatments have been proposed to address the problem of contamination. one person The method involves preparing a composition containing a sulfonated phenol-formaldehyde condensation product. It is used as a base material. However, sulfonated phenol-formal The dehyde condensation product itself is subject to discoloration and usually turns yellow. The problem with yellowing is r Rev of the March 19, 1932 issue of America's Textiles ersibleYellowing Not Finisher’s Fault W, H0He+npel in the document entitled tJ. He5 npel is a phenol-based finish that contains nitrogen oxide and/or purple The yellowing is attributed to exposure to outside radiation. To deal with the problem of yellowing For this reason, the above condensation product is phenolic in U, S, 4,936.409. By acylating or etherifying the hydroxyl group, Li Modified by 5s et al. December 1991, of which this application is a continuation in part The inventor's U.S. Patent Application No. 07/809.843, received on the 18th, describes Water-soluble or water-dispersible maleic anhydride/alpha olefin for dyeability Discloses a polyamide fiber substrate treated with a polymer and a method for producing the same. And they are filing a patent claim. Stain-resistant poria treated with the composition of the invention The mid-base material is disclosed in the inventor's concurrent application, ^ttorney Do, which was accepted on the same date. No. Cl-2261.

Brief description of the invention The present invention (j) Water-soluble or water-dispersible alpha olefin/maleic anhydride polymer or a mixture of this polymer and (n) a dye fastener, a fixing agent, a dye remover; (dye reserving agent) or dyeing resistance of polyamide fibers Sulfonated phenol-formaldehyde condensation useful as a wetness improving agent Provides compositions useful for imparting stain resistance to polyamide fiber substrates, including products do.

The composition of the present invention can be used for shampoo cleaning of polyamide substrates treated thereby. This shows that the durability against Furthermore, the present invention provides ultraviolet rays or NOX gas. yellowing than sulfonated phenol/formaldehyde condensates when exposed to To provide an antifouling agent that is more resistant to stains. At least some aspects of the invention It has good stain resistance, low yellowing tendency and good substantivity. Attempts are made to provide stain-resistant compositions that can provide the desired stain resistance. Compositions with conventional technology Another problem with this is that unless surfactants are used, It has low solubility in water at low pH, which is preferred for use. The present invention In at least some embodiments, the present invention provides stain resistant compositions that have good water solubility. An attempt is made to provide a gift.

The two components may be mixed together in a wide range of relative proportions.

For example, the weight ratio of maleic anhydride copolymer to resin is about 95:5 to 5:95; Desirably about 90:10 to about 10:90, more preferably about 60+ It may be within the range of 40-40:60. The pH of this formulation is desirably adjusted by acid to the required p in the range of about 1 to 3, more preferably 1.5 to 2.5. It will be done. Surprisingly, the stain resistant compositions of the present invention at such low pH Remain transparent. This discovery indicates that the stain-resistant composition of the present invention dissolves the active ingredient. Advantageously, it is not necessary to contain any surfactants to achieve the desired results. however, If desired, the composition may contain a surfactant. higher ranging from about 7 to 9 pt+ can also be adopted.

Maleic Anhydride/Alpha Olefin Polymers Polymers Useful for the Purposes of the Invention contains one or more hydrolyzed anhydrous maleates, either soluble or non-dispersible. Contains phosphoric acid polymers.

A variety of linear and branched alpha olefins can be used for the purposes of this invention. Ru. Particularly useful alpha olefins are butadiene, chlorobrene, isoprene, and 2-methyl-1,5-hexadiene. Diene: such as isobutylene, 1-butene, 1-hexane, 1-octene, etc. 1-alkenes containing 4 to 8 carbon atoms, with isobutylene being most preferred. a Some of the Rufer olefins contain other monomers such as up to 50% by weight of alkyl (c , -C4) acrylate, alkyl (C+-C<) tamacrylate, vinyl sal Fido, N-vinylpyrrolidone, acrylonitrile, acrylamide and It may be replaced by a mixture of these.

A portion of the maleic anhydride (preferably 1 to 75% by weight) is a maleimide, N-alkyl (C+~C<)maleimide, N-phenyl-maleimide, fumaric acid, itacon acids, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyls of these acids (C+~C08) esters, cycloalkyl (CS-Cs) esters of these acids It may be replaced by oil, sulfated castor oil, etc. Maleic anhydride copoly At least 95% by weight of the polymer or terpolymer is about 700-200.000 , preferably in the range of about 1,000 to ioo, ooo.

Maleic anhydride polymers useful in the present invention can be made according to methods well known in the art. Ru. The maleic anhydride polymer thus obtained is mixed with water or an aqueous alkaline solution. can be hydrolyzed to the free acid or its salt by reaction, or C,- Polymers that can be reacted with C4 alkyl alcohols and have contamination blocking properties --like alpha olefin/maleic anhydride monoester is produced.

Polymers suitable for the purposes of the present invention include polymeric units derived from maleic anhydride. Polymers derived from one or more alpha olefins Contains about 0.7 to 1.3 mer units. The alpha olefin content of the polymer of the present invention (a) at least one 1-alkene containing 4 to 8 carbon atoms or is 100 mol% to 8 for terminally unsaturated dienes containing 4 to 18 carbon atoms. 0 mol % and (b) less than 3 or 10 to 18 carbon atoms (both one) 0 to 20 mol% of the 1-alkene. Derived from maleic anhydride from one or more olefin monomers per polymer unit Polymers containing about one derivatized polymer unit provide stain resistance to textile substrates. It is also the most effective for achieving The molecular weight of the polymers useful in this invention is such that the polymer is This does not seem to be a limitation as long as it is soluble or water-dispersible. Therefore, the analogy isobutylene/anhydrous having a number average molecular weight of about 6.000 to 100.000. Hydrolyzed copolymers of maleic acid have good stain resistance on polyamide substrates. Gives dyeability. Even at pm as low as 1.5, about 6.000-100,0 Water-soluble isobutylene/maleic anhydride copolymer with a number average molecular weight of 0.00 remained in solution form in water at 60°C.

Polymers suitable for the purposes of the present invention include maleic anhydride/ It can be produced by hydrolyzing olefin polymers. For example, this poly The mer can be hydrolyzed to the free acid or its salt by reaction with water or an alkali. It's fine.

A preferred maleic anhydride polymer is an isobutylene/anhydride with a molecular weight of about io, ooo. water maleic acid copolymer rIsoba-01, molecular weight approximately 40,000 "l5oba■"-04, which is a similar polymer with a molecular weight of about 100, A similar polymer, rIsobamJ-10, with 000 It can be easily obtained by hydrolysis with Another suitable anhydrous Malay The acid polymer includes B-30, available from Kuraroy Co., (Japan). be. B-30 is an isobutylene/anhydrous maleic acid having a molecular weight of approximately 40,000. phosphoric acid/N-phenylmaleimide terpolymer. used without further processing. Commercially available products that can be used include rLindronJ 10 (Linda u Chemical), i.e. about 5,000 to 10,000 molecules. butadiene/maleic anhydride copolymer having an amount of Other suitable copolymers 04-C8 alpha olefin/maleic anhydride copolymer monoester There is a tell. This monoester is within a range well known to those skilled in the art. It can be obtained by A preferred method is with alcohol under reflux. By heating to react and then removing excess alcohol. Preferred a Alcohols are C,-C4 alcohols, especially methanol and ethanol.

The production of maleic anhydride/alpha olefin polymers is covered by U.S. Reissue Patent No. No. 8.475, EP 306992 and Florjanczyk et al., J.

Polymer SC1, Part A, Polymer CheIll, 27(12), pages 4099-4108. this et al., the disclosures of which are specifically incorporated herein by reference. These references can be found here It also includes further teachings on techniques for making such polymers.

Sulfonated phenol-formaldehyde resins that can be used for the purposes of the present invention The sulfonated phenol-formaldehyde condensation product may be treated with dye fasteners or fibres. as a dye removal agent or wet fastness agent or for polyamide fibers. has been shown in the prior art to be useful as an agent to improve staining on fibers. There are any sulfonated hydroxyaromatic-formaldehyde condensation products. example U, S, 4,592,940, U, S, 4,591,591, U, S.

3,790.344 and GO1,291,784. These features The disclosures of No. City suitable for the present invention The commercially available condensation product is IESITOL NBS, a product of Bayer AG. (4-hydroxyphenyl)-sulfone, formaldehyde and phenol Condensation products made from sulfonic acids; u, s, 3,790,344) and rErionalJ NW, a product of Giba-Geigy Corp. (naphthalene monosulfonic acid, bis(hydroxyphenyl)sulfone and phorol) By condensing a mixture of maldehydes, U, S.

3, 716.393) and rErional JLY. Cybron Also ^1lied by Chemicals as rStainfroeJ Co11oid Co, sold as [^Igard JNS] Also suitable are sulfonated hydroxyaromatic formaldehyde products.

application Stain-resistant compositions can be prepared in a variety of ways known to those skilled in the art, e.g. ding, spraying, simultaneous forming with forming agent, Beck staining By batch exhaustion in the device or by continuous exhaustion during continuous dyeing operations, It can be efficiently applied to polyamide fiber substrates. The stain-resistant composition of the present invention is They can be applied to the substrate individually or together in a mixture. In the case of the present invention, The stain resistance of polyamide substrates is due to the fact that the maleic anhydride/olefin polymer The sulfonated phenol/formaldehyde condensate is then applied to the substrate. If so, it will be slightly better. Carpet factories, on the other hand, apply the ingredients of stain-resistant mixtures together. and therefore would expect the compositions of the present invention to do so as well. Dew.

The stain-resistant composition of the present invention can be applied to dyed or undyed textile substrates by the method described above. can be administered. Additionally, the composition contains a polyfluoroorganic oil, water and ( or) without repellent materials or It may be applied to substrates such as those described above in the presence of these substances. Alternatively, this The polyfluoro-organic material, such as After that, it can be applied to a textile substrate.

If the stain-resistant composition is applied to a textile substrate at 20°C, then heat treatment at a temperature in the range of about 1 to 60 minutes, or at a temperature in the range of about 40 to 95 degrees Celsius for about 1 to 60 minutes. If applied to a textile substrate, contamination can be blocked more effectively. For example, about 2-3 A temperature of about 70-90°C in pn is preferred.

However, even when applied at cold tap water temperatures (10-15°C), contamination can be blocked.

The stain-resistant composition of the present invention can be applied to pots already installed in homes, offices or other locations. It can also be applied to Liamido carpets on the spot. The composition may include one or more A pot containing more polyfluoro-organic oil, water and/or soil protection substances. applied as a simple aqueous formulation without or in the form of an aqueous shampoo formulation. can be done. The composition is prepared at temperatures as described above and from about 1 to 9, preferably from about 2 to 9. At a pH of 7, it may be applied at the levels mentioned above.

In the examples below, all viscosities were measured at room temperature of about 20°C and all All percentages are by weight and the following application and testing methods were employed.

Method of application 70 oz/sq yd superba-set BCF A cut pile dyed bright blue made from nylon 66 was used in the example. Using a solution of antifouling agent at pH 2.0 as described in In the presence of 2.0 g of magnesium sulfate, the liquid to product ratio was 20:1. Textiles were processed in a laboratory Beck apparatus for 20 minutes at 0°C (176°F). The application loading rate is 0.8% based on the active ingredient. Then water the carpet Rinse with tap water, partially dehydrate by wringing and force air oven Dry at 121°C (250°F) for approximately 20 minutes. Adhesive for carpet backing material A commercially available latex composition (Text from Ca1houn, Georgia) ile Rubber Co.) with the product name of ＾ctionbac. With propylene's second backing material, MOCO from ^tlanta, Georgia. provided.

contamination test A carpet swatch (3 x 5 inches) was placed on a non-absorbent flat surface. FD & Contains Red Dye No. 40, has a cherry aroma and is sweetened with sugar. Commercially available dilutable soft drink with 459 and water 500mj' and Karatsu The resulting solution was injected into a 2-inch diameter cylinder tightly attached to a 20d1 sample. . After all the liquid was absorbed, the cylinder was removed. contaminated carpet sample Leave it on for 24 hours, then rinse thoroughly with cold tap water. I squeezed it dry. Inspect the specimen visually and according to the following contamination rating scale: The degree of color remaining in the contaminated area was evaluated.

5=no contamination 4 = slight pollution 3 = Visible contamination 2 = significant pollution 1 = severe pollution In other words, a stain rating of 5 is excellent, indicating significant stain resistance, while a rating of 1 is Shampoo cleaning durability test with the same worst rating as the untreated control sample Duponol WAQE (1.5 q per 11) and dilute charcoal 3x in a detergent solution whose pH was adjusted to 10 ± 0.1 with sodium A 5 inch carpet swatch was soaked for 5 minutes at room temperature. Next, take out the sample and water it with water. Rinse thoroughly under a stream of tap water, dehydrate by squeezing and in the air. Dry. The dry carpet swatches were then tested according to the stain test described above. .

UV lightfastness TCC test method for color fastness against ultraviolet rays Measured according to Act 16E-1987. 40^ATCC fading device (^FLI) After exposure, the swatches were evaluated using a gray scale for color change.

NOX light resistant type light hardening Color fastness to nitrogen oxide according to TCC test method 164-1987 was measured. According to the gray scale regarding the color change at the end of two cycles Samples were evaluated.

A stain-resistant carpet was obtained by the treatment according to the invention. Furthermore, the main Carpets washed with shampoo after application of light anti-stain agent but before staining still had a high degree of stain resistance.

Example 1 A solution of 649.5 q of sodium hydroxide in 5184 g of demineralized water at 40°C was Commercially available as rIsobaJ-01 from the book Kuraray Carp. Hand-made isobutylene-maleic anhydride copolymer with molecular weight 10.000 -2,500q was slowly added with stirring. The heat generated during hydrolysis increases the temperature. The temperature reached 70-90°C. The reactants were kept at 80-85°C for about 15-20 hours. Thereafter, it was cooled to 65°C. Add a 30% solution of sulfuric acid to a clear, brownish solution at 14%. 57.59 was added under stirring. The pH dropped to 2.65. Cooled to approximately 55℃ Later, from Ciba-Geigy Carp, entered as rErional JLY. Hand-made sulfonated hydroxy-aromatic formaldehyde condensation products 1,764 ．． 79 to the above clear, amber colored solution with stirring and determine the active ingredient content. is about 25%, pt+ is 2.61 and viscosity is 286 Pa·sec. A brownish solution 11764.8'9 was obtained. 12 of sulfuric acid to the 1% solution of Example 1. % solution, no precipitation occurred at pn as low as 1.5.

Example 2 In a solution of 259.7 q of sodium hydroxide in 207.69 q of deionized water at 60°C , commercially available as rIsobaIIJ-04 from Kuraray Carp, Japan. isobutylene-maleic anhydride having a molecular weight of about 40,000, available from 1000 q of copolymer was added slowly with stirring. 80~ Stirred at 85°C for 18 hours. Next, add the deionized liquid to this transparent and colored liquid. A solution of 683.3 q of a 30% solution of sulfuric acid in 983.39 ml of water was brought to 60°C. ) with stirring, the active ingredient content is 20%, and the viscosity is 606 Pa. A clear product was obtained with pl+2.40 seconds. prepared by the method described above 400 g of polymer from Ciba-Geigy Corp. Sulfonated hydroxy aromatic-formaldehyde condensate available as lJLY The synthesis product was added with stirring at room temperature. Clear, brownish liquid active substance The content was 20.8%. A 1% solution was prepared with dilute sulfuric acid to bring the pF to 1. After adjusting to 5, it remained clear.

Example 3 Sodium hydroxide in 622.1 q of deionized water at 40°C? 7.9 q of solution , commercially available as rIsobasJ-01 from I[uraray Corp., Japan. The commercially available isobutylene-maleic anhydride copolymer 3009 was slowly Added. Due to the exotherm during hydrolysis, the temperature reached 70-90°C. reactants It was kept at 80-85°C for about 15-20 hours. After cooling to 60°C, deionization of 809 208.6 q of a 30% sulfuric acid solution in water was added with stirring until the active ingredient was ．． 3%, has a pH of 2.47 and a viscosity of 340 Pa·s. An amber colored solution was obtained. 364,89 pot prepared by the method described above. To Rimmer, “5tainfreeJ” from Cybron Che+eicals (30% active ingredient), sulfonated hydroxyaromatic-formamyl 50 g of the aldehyde condensate was added at room temperature with stirring to obtain a concentration of about 24.1% active ingredient. A clear brownish product was obtained. This substance can be used at any desired concentration at a pH of Remained clear when applied at 2.0.

Example 4 Poly? used in Example 3? -364,89, A11ied Co11oid C sulfonate, available as ^Igard JNS (30% active ingredient) from 509 hydroxyaromatic-formaldehyde condensation product with stirring at room temperature. was added to give a clear brownish liquid with about 24.1% active ingredient. this thing The quality remained clear at any desired concentration at ptl2.0.

Example 5 207, 26 in deionized water of 49. Japan in a solution of Oq sodium hydroxide Commercially available as [l5obaJ-Ql] from Kuraray Co. 100 isobutylene-maleic anhydride copolymer having a molecular weight of 10.000 9 Add slowly at 50° C. with stirring. rMEsIT from Bayer AG Sulfonated hydroxyaromatic available as OLJNBS (30% active ingredient) -Formaldehyde condensate 58.89 and sodium hydroxide in deionized water 759.39 A solution of 24.79% of a 30% solution of thorium was added under stirring until the pH was 8.55. 1176, a transparent brownish liquid with an active ingredient content of 10.0%, I got 29. The 1% solution becomes clear after adjusting the PTL to 2.0 with dilute sulfuric acid. It remained untouched.

Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, NiC, NL, P T, SE), AU, CA, FI, JP, -KR, N.

Claims (1)

[Claims] 1. (A) one polymer unit derived from maleic anhydride, one or About 0.7 to 1 polymer units derived from alpha olefins ．． 3 containing water-soluble or water-dispersible alpha olefins/maleic anhydride polymers. remer or mixture thereof, the alpha olefin content of the polymer (i) at least one 1-alkene or carbon containing 4 to 8 carbon atoms; 100 mol % to 80 mol % for terminally unsaturated dienes containing 4 to 18 atoms and (ii) at least one carbon atom containing 3 or 10 to 18 carbon atoms. from 0 to 20 mol % of 1-alkene or mixtures thereof. things and (B) Contains a sulfonated phenol-formaldehyde condensation product, which is a combination of A and B. Stain resistant for polyamide fiber substrates with a weight ratio in the range of 5:95 to 95:5 Compositions that help give sex. 2. The composition of claim 1, wherein the weight ratio is about 90:10 to 10:90. 3. The composition of claim 1, wherein the weight ratio is in the range of about 60:40 to 40:60. 4. At least 95% by weight of the maleic anhydride polymer is about 700 to 200,0 The composition of claim 1 having a number average molecular weight of 0.00. 5. At least 95% by weight of the maleic anhydride polymer is about 1,000 to 100% 5. The composition of claim 4 having a number average molecular weight of ,000. 6. the polymer is derived from one or more alpha olefin monomers For each polymer unit derived from maleic anhydride, 6. The composition of any one of claims 1-5, comprising about one. 7. The composition of claim 6, wherein at least one of the 1-alkenes is isobutylene. . 8. Up to 50% by weight of the alpha olefin is one or more C1~ C4 alkyl acrylate or methacrylate, vinyl acetate, vinylc loride, vinylidene chloride, vinyl sulfide, N-vinylpyrrolidone , acrylonitrile or acrylamide or mixtures thereof. The composition of claim 1, wherein the composition has been changed. 9. Up to 75% by weight of maleic anhydride is maleimide, N-alkyl (C1-C 4) Maleimide, N-phenylmaleimide, fumaric acid, itaconic acid, citracone acids, aconitic acid, crotonic acid, cinnamic acid, alkyl of these acids (C1-C18 ) or by cycloalkyl (C3-C6) esters or sulfated castor oil. 2. The composition of claim 1, wherein the composition is replaced. 10. Up to 30% by weight of maleic anhydride can be replaced by acrylic or methacrylic acid. 2. The composition of claim 1, wherein the composition is replaced by 11. (A) One or more per polymer unit derived from maleic anhydride. contains polymer units derived from more alpha olefins from about 0.7 to 1.3 Containing water-soluble or water-dispersible alpha olefins/maleic anhydride a polymer or mixture thereof, the alpha olefin-containing polymer (i) at least one 1-alkene containing 4 to 8 carbon atoms; or 100 mol% to 80 for terminally unsaturated dienes containing 4 to 18 carbon atoms (ii) at least one containing 3 or 10 to 18 carbon atoms; of 0 to 20 mol % of the 1-alkene, or mixtures thereof. compound and (B) Contains a sulfonated phenol-formaldehyde condensation product, which is a combination of A and B. Provides stain resistance to a polyamide fiber substrate with a weight ratio in the range of 5:95 to 95:5. A polyamide fibrous substrate having deposited thereon an amount of a composition effective to increase 12. 12. The substrate of claim 11, wherein the weight ratio is about 90:10 to 10:90. 13. 12. The substrate of claim 11, wherein the coulometric ratio is in the range of about 60:40 to 40:60. 14. At least 95% by weight of the maleic anhydride polymer is about 700-200%, 12. The substrate according to claim 11, having a number average molecular weight of 0.000. 15. At least 95% by weight of the maleic anhydride polymer is about 1,000 to 10 15. The substrate of claim 14 having a number average molecular weight of 0,000. 16. The polymer is derived from one or more alpha olefin monomers. For each polymer unit derived from maleic anhydride, 16. The substrate of any one of claims 11-15, comprising about one. 17. The group according to claim 16, wherein at least one of the 1-alkenes is isobutylene. Material. 18. Up to 50% by weight of the alpha olefin is one or more C1 ~C4 alkyl acrylate or methacrylate, vinyl acetate, vinyl Chloride, vinylidene chloride, vinyl sulfide, N-vinyl biloride acrylonitrile or acrylamide, or mixtures thereof. The substrate according to claim 11, which has been replaced. 19. Up to 75% by weight of maleic anhydride is maleimide, N-alkyl (C1- C4) Maleimide, N-phenylmaleimide, fumaric acid, itaconic acid, citraco aconitic acid, crotonic acid, cinnamic acid, alkyl of these acids (C1-C1 8) or by cycloalkyl (C3-C8) ester or sulfated castor oil. 12. The substrate according to claim 11, wherein the substrate is replaced. 20. Up to 30% by weight of maleic anhydride can be replaced by acrylic or methacrylic acid. 12. The substrate according to claim 11, wherein the substrate is replaced. 21. (A) One or more per polymer unit derived from maleic anhydride. contains polymer units derived from more alpha olefins from about 0.7 to 1.3 Containing water-soluble or water-dispersible alpha olefins/maleic anhydride a polymer or mixture thereof, the alpha-olefin-containing polymer (i) at least one 1-alkene containing 4 to 8 carbon atoms; or 100 mol% to 80 for terminally unsaturated dienes containing 4 to 18 carbon atoms (ii) at least one containing 3 or 10 to 18 carbon atoms; of 0 to 20 mol % of the 1-alkene, or mixtures thereof. compound and (B) The sulfonated phenol-formaldehyde condensation product is added to a polyamide fabric. to this substrate together or separately in amounts effective to impart stain resistance to the substrate. and the weight ratio of A and B is in the range of 5:95 to 95:5. , a method for imparting stain resistance to polyamide woven substrates. 22. 22. The method of claim 21, wherein the weight ratio is about 90:10 to 10:90. 23. 22. The method of claim 21, wherein the weight ratio is in the range of about 60:40 to 40:60. 24. At least 95% by weight of the maleic anhydride polymer is about 700-200%, 22. The method of claim 21 having a number average molecular weight of 0.000. 25. At least 95% by weight of the maleic anhydride polymer is about 1,000 to 10 25. The method of claim 24, having a number average molecular weight of 0,000. 26. the polymer is derived from one or more alpha olefin monomers For each polymer unit derived from maleic anhydride, 26. The method of any one of claims 21-25, comprising about one. 27. The method according to claim 26, wherein at least one of the 1-alkenes is isobutylene. Law. 28. Up to 50% by weight of the alpha olefin is one or more C1 ~C4 alkyl acrylate or methacrylate, vinyl acetate, vinyl Chloride, vinylidene chloride, vinyl sulfide, N-vinyl biloride acrylonitrile or acrylamide or mixtures thereof. 22. The method according to claim 21, wherein the method is replaced. 29. Up to 75% by weight of maleic anhydride is maleimide, N-alkyl (C1- C4) Maleimide, N-phenylmaleimide, fumaric acid, itaconic acid, citraco aconitic acid, crotonic acid, cinnamic acid, alkyl of these acids (C1-C1 8) or by cycloalkyl (C3-C8) ester or sulfated castor oil. 22. The method of claim 21, wherein the 30. Up to 30% by weight of maleic anhydride can be replaced by acrylic or methacrylic acid. 22. The method of claim 21, wherein the