EP0329899A2 - Polymères aromatique/anhydride maléique résistant aux salissures - Google Patents
Polymères aromatique/anhydride maléique résistant aux salissures Download PDFInfo
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- EP0329899A2 EP0329899A2 EP88311835A EP88311835A EP0329899A2 EP 0329899 A2 EP0329899 A2 EP 0329899A2 EP 88311835 A EP88311835 A EP 88311835A EP 88311835 A EP88311835 A EP 88311835A EP 0329899 A2 EP0329899 A2 EP 0329899A2
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- Prior art keywords
- polymer
- maleic anhydride
- stain
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Definitions
- the present invention relates to polyamide textile substrates treated with stain-resistant compositions comprising hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers, and processes for their preparation.
- the substrates of this invention possess stain resistance but do not suffer from yellowing to the extent that previously known materials do.
- Polyamide substrates such as nylon carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages.
- An especially troublesome staining agent is FD&C Red Dye No. 40, commonly found in soft drink preparations.
- Different types of treatments have been proposed to deal with staining problems.
- One approach is to apply a highly fluorinated polymer to the substrate.
- Another is to use a composition containing a sulfonated phenol-formaldehyde condensation product.
- Liss and Beck in U.S. Patent Application Serial No. 124,866, filed 23 November 1987, disclose stain-resistant synthetic polyamide textile substrates having modified sulfonated phenol-formaldehyde polymeric condensation products.
- sulfonated phenol-formaldehyde condenation products are themselves subject to discoloration; commonly they turn yellow.
- Yellowing problems are described by W. H. Hemmpel in a March 19, 1982 article in America's Textiles , entitled Reversible Yellowing Not Finisher's Fault . Hemmpel attributes yellowing to exposure of a phenol-based finish to nitrogen oxides and/or ultraviolet radiation.
- Allen et al. in U.S. Patent 3,835,071, disclose rug shampoo compositions which upon drying leave very brittle, non-tacky residues which are easily removed when dry.
- the compositions comprise water-soluble metal, ammonium or amine salt of a styrene-maleic anhydride copolymer, or its half ester, and a detergent.
- Water-soluble metal salts of Group II and the alkali metals (particularly magnesium and sodium) are preferred and ammonium salts are most preferred by Allen et al.
- the present invention provides polyamide textile substrates treated with hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers so as to impart stain resistance to the substrates, and methods for preparing the same.
- Commonly materials known in the past to be useful as stain blockers were sulfonated. Finding a non-sulfonated material, such as the hydrolyzed ethylenically unsaturated aromatic/maleic anhydride of this invention, to be useful for this purpose was unexpected.
- the hydrolyzed polymers suitable for the purposes of this invention contain between about one and two polymer units derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride (hydrolyzed polymers containing three ethylenically unsaturated aromatic polymer units per maleic anhydride polymer unit are not suitable). Hydrolyzed polymers containing about one polymer unit derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride are most effective in imparting stain resistance to textile substrates. A variety of ethylenically unsaturated aromatic compounds can be used for the purpose of preparing the hydrolized polymers of this invention.
- aromatic compounds can be represented by the formula Specific examples of ethylenically unsaturated aromatic compounds suitable for the purposes of this invention include styrene, alpha-methylstyrene, 4-methyl styrene, stilbene, 4-acetoxystilbene (used to prepare a hydrolized polymer from maleic anhydride and 4-hydroxystilbene), eugenol, isoeugenol, 4-allylphenol, safrole, mixtures of the same, and the like. From the standpoint of cost-effectiveness, a copolymer prepared from styrene and maleic anhydride at a 1:1 molar ratio is preferred.
- the hydrolyzed polymers can have molecular weights (number average) in the range between about 500 and 4000, preferably between about 800 and 2000. They are readily soluble, even at high concentrations, in water at neutral to alkaline pH; increasing dilution is needed at a pH below 6. They are also soluble in lower alcohols, such as methanol, and are somewhat soluble in acetic acid.
- the polymers suitable for the purposes of this invention can be prepared by hydrolyzing ethylenically unsaturated aromatic/maleic anhydride polymers. However, not just any hydrolyzing agent will give products of equivalent utility for the purposes of this invention.
- Alkali metal hydroxides are suitable hydrolyzing agents. While potassium and/or lithium hydroxides can be subtituted for sodium hydroxide in whole or in part as a hydrolyzing agent, the latter is preferred. Hydrolysis can be effected in the presence of more than or less than a molar amount of an alkali metal hydroxide, such as NaOH.
- hydrolysis of the polymer in the presence of ammonium hydroxide gives a product which does not provide satisfactory stainblocking properties to a polyamide textile substrate.
- the polymer is hydrolyzed in the presence of ammonium hydroxide, it is essential that it be held at elevated temperature for an extended period of time thereafter; otherwise, the polymer imparts unsatisfactory stainblocking properties to polyamide substates.
- hydrolysis of the polymer in the presence of excess ammonium hydroxide results in a product which fails to impart satisfactory stainblocking properties to polyamide substrates even after having been held for an extended period of time at elevated temperature. Neither should hydrolysis be carried out in the presence of an alcohol.
- the ethylenically unsaturated aromatic/maleic anhydride polymer can react with the alcohol to form a half-ester which will be deleterious to the stain-resist performance of the hydrolyzed polymers.
- the hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers of this invention can be used as such in treating polyamide textile substrates. They can be applied to dyed or undyed polyamide textile substrates. They can be applied to such substrates in the absence or presence of a polyfluoroorganic oil-, water-, and/or soil-repellent materials. In the alternative, such a polyfluoroorganic material can be applied to the textile substrate before or after application of the hydrolyzed polymers of this invention thereto.
- the hydrolyzed polymers can be applied to textile substrates in a variety of ways, e.g. during conventional beck and continuous dyeing procedures.
- the quantities of the polymers of this invention which are applied to the textile substrate are amounts effective in imparting stain-resistance to the substrate.
- the amounts can be varied widely; in general, one can use between 0.1 and 2% by weight of them based on the weight of the textile substrate, usually 0.6% by weight or less.
- the polymers can be applied, as is common in the art, at pHs ranging between 4 and 5. However, more effective exhaust deposition can be obtained at a pH as low as 2. When pH of 2 is used, the preferred level of application to the textile substrate is about 0.6% by weight, based on the weight of the textile substrate. More effective stainblocking is obtained if the hydrolyzed polymers are applied to the textile substrate at higher temperatures. For example, at pH 2, 170°F is preferred, and 200°F is preferred at pH 5. However, stainblocking can be obtained when application is effected at room temperature, or even at that of cold tap water (10-15°C).
- the hydrolyzed polymers of this invention can also be applied in-place to polyamide carpeting which has already been installed in a dwelling place, office or other locale. They can be applied as a simple aqueous preparation or in the form of aqueous shampoo preparation, with or without one or more polyfluoroorganic oil-, water-, and/or soil-repellent materials. They may be applied at the levels described above, at temperatures described, and at a pH between about 1 and 12, preferably between about 2 and 9.
- stain-resists to carpeting is carried out in a Launder-O-Meter automated dyeing machine.
- One carpet piece is contained in each of several (up to twenty) stainless steel, screw-cap canisters.
- the canisters are held in a rack that rotates in a water bath whose temperature is automatically controlled for rate of heating, time at temperature and cooling.
- For a typical application bath one uses a 20 to 1 liquor to goods ratio with 2.5 weight % of the stain-resistant composition.
- the stain-resistant compositions can be applied at pH 2 or pH 5. At pH 2, an excess of sulfamic acid is used.
- an excess of ammonium sulfate is used, as well as 3g/L of magnesium sulfate and lg/L of an alkyl aryl sulfonate (Alkanol®ND) or a suitable leveling agent.
- a solution of the stain-resist composition is added to the Launder-o-Meter canister.
- the carpet sample to be treated is then placed in the canister, tufted side out, the size of the carpet sample, relative to the size of the canister, being such that the no portion of the sample touches another portion of the sample.
- the canisters are placed in the Launder-O-Meter and the water bath temperature is held at 110°F for 5 minutes.
- the temperature of the water bath is then raised to the desired temperature for application of the stain-resist composition.
- the temperature of the water bath is raised to 170°F ⁇ 5°F, and for application at pH 5, the temperature of the water bath is raised to 200°F ⁇ 5°F.
- the bath water reaches the desired temperature, it is held there for 20 min. and then cooled to 100°F.
- the treated carpet sample is removed from the canister and rinsed by squeezing in deionized water at room temperature. Three successive rinses in fresh deionized water are given, each rinse being at 40 volumes of water per volume of sample.
- the rinsed carpet sample is centrifuged to remove excess liquid and dried at 200°F. in a forced draft oven for 30 minutes. The dry carpet sample can then be tested by use of the tests described below.
- Stain Test A is used to measure the extent to which carpeting is stained by a commercial beverage composition which contains FD&C Red Dye No. 40 (an acid dye).
- the staining liquid if sold commercially as a liquid, is used as is.
- the commercial product is in the form of a solid.
- the beverage preparation in dry, solid form, is dissolved in deionized water so as to provide 0.1 g of FD&C Red Dye No. 40 per liter of water.
- Sufficient wetting agent Du Pont Merpol®SE liquid nonionic ethylene oxide condensate
- test sample is Dupont type 1150 Nylon 6,6 (white); Superba heatset, mock dyed level loop carpet, 3/8 inch pile height, 30 ounces per yard, 1/10 inch gauge, 10 stitches per inch, woven polypropylene primary backing.
- the test sample is wetted completely with water, and excess water is removed by centrifuging.
- the damp sample is placed tufted face down in a pan and covered with ten times its face weight of stain fluid. Entrained air is expelled from the sample by squeezing or pressing. The sample is turned over and again the air is expelled. The sample is then returned to a face down position, and the pan is covered for storage for desired test period, namely 30 minutes or 24 hours.
- the stored stain sample is rinsed in running cool water until no more stain is visually detectable in the rinse water.
- the rinsed sample is extracted in a centrifuge and dried at 200 degrees F. Staining is evaluated with the Minolta Chroma Meter tristimulus color analyzer in the L*A*B Difference Mode with the target sample set for the unstained carpet.
- the "a" value is a measure of redness, with a value of 43 equal to that obtained on an untreated carpet.
- Stain Test B a 6 inch x 6 inch (15 cm x 15 cm) specimen of carpet is placed on a flat non-absorbent surface. 20 ml of the staining fluid described in Stain Test A is applied to the specimen of carpet by placing a 1-1/2 inch x 2 inch (3.8 cm x 5.1 cm) cylinder tightly over the specimen and pouring the staining liquid solution into the cylinder to contact the carpet specimen thereby forming a circular stain. The cylinder is then removed and excess staining solution is worked into the carpet tufts to achieve uniform staining. The stained carpet specimen is left undisturbed for 24 ⁇ 4 hours, after which it is rinsed thoroughly with cool water, squeezed dry, and excess solution removed.
- the light-fastness of carpet samples treated with a stainblocker is determined by exposing the treated samples to UV light for 20 Hours.
- a sample piece of carpet that has been treated with a stain-blocker is placed in a box containing its hinged top a standard fluorescent fixture fitted with two forty watt lamps. Centered under the pair of lamps in the bottom of the box is a sliding tray having a 3 inch x 40 inch recess for holding carpet specimens. The depth of the recess is such that the distance from the carpet face to the plane defined by the lamp surfaces is 1 inch.
- the current to the lamp is controlled by a timer so that a twenty-hour exposure can be obtained automatically.
- the reflectance of CIE White Light Source C from the carpet is compared with the reflectance from an unexposed sample and the CIELAB delta “b” noted.
- Delta “b” is a measure of the yellow component of white light.
- a Minolta Chroma Meter model CR-110 reflectance meter is used to make the measurements and to calculate delta "b” automatically from stored data on the unexposed sample. The value of "b” is reported as the measure of yellowing with increasing positive values of "b” corresponding to increased degrees of yellowing.
- the Minolta Chroma Meter is used in the Hunter L*a*b color-deviation measuring mode [Richard Hunter, "Photoelectric Colorimetry with Three Filters,” J. Opt. Soc. Am., 32 , 509-538 (1942)].
- the instrument measures the color differences between a "target” color, whose tristimulus color values have been entered into the microprocessor as a reference, and the sample color presented to the measuring head of the instrument.
- the "target" color entered is that of the carpet before yellowing or staining.
- the color reflectance of the yellowed or stained carpet is then measured with the instrument and reported as: *E, the total color difference, *L, the lightness value, *a, the redness value, if positive, or greenness, if negative, and *b, the yellowness value, if positive, or blueness, if negative.
- Example 1 was repeated using 2460 g. of ammonium hydroxide solution (28% NH3) instead of the 5400 g. of sodium hydroxide. A product similar in appearance to the product from Example 1 was obtained. However, it provided little or no stain resistance in the 1/2 hr. Stain Test described above.
- Example 3 was repeated using stilbene (20.0 g., 0.21 mols) and maleic anhydride (10.9 g., 0.21 mols), and dodecyl mercaptan (2.3 g., 0.011 mols). There obtained 29.2 g. of white polymer which on hydrolysis provided a white opaque dispersion with limited water solubility.
- the carpet was cleaned in three passes with a 1:150 diluted shampoo (described below) using a Stanley Steemer truck mount. The carpet was treated in this manner "in place” at room temperature and was allowed to dry at room temperature.
- PGME Propylene glycol monomethyl ether
- DPM Dipropylene glycol monomethyl ether
- Fluorosurfactant A mixture of Li fluoroalkyl mercapto propionate and diethanolammonium fluoroalkyl phosphate in a 1.0:1.1 ratio.
- Methyl isobutyl ketone (951.3 g) in a 4-neck 2.0 L flask fitted with mechanical agitation, condenser, temperature controller, nitrogen bubbler and heating mantle was heated to 70°C and sparged with nitrogen for one hour then cooled to room temperature.
- maleic anhydride 98.06 g, 1.0 mol
- stilbene 45.06 g, 0.25 mol
- styrene 78.11 g., 0.75 mol
- dodecylmercaptan (16.6 g., 0.082 mol). This mixture was heated to a steady 70°C with stirring under a nitrogen sweep.
- VAZO® 67 initiator [2,2′-azobis--(2-methylbutyronitrile)] (2.21 g, 0.0115 mol) was then added in one portion as a solid, no appreciable exotherm was noticed.
- the reaction was stirred at 70°C for 3 hours then additional VAZO® 67 (1.1 G, 0.0057 mol) was added.
- the reaction continued to stir at 70°C for another 3 hours, then it was cooled to room temperature. Approximately 3/4 of the MIBK was then removed by rotary evaporation (or vacuum distillation at 10 mmHg).
- petroleum ether ca . 1 L
- the product solution thus obtained was applied to nylon carpet at 5 percent (1 percent active ingredient) on weight of fiber in a simulated beck dyeing apparatus at a pH of 2.0.
- the dried carpet was tested by saturating it with a solution of FD&C Red Dye No. 40 and letting it stand for 24 hours at room temperature. It was then rinsed with cold water.
- the treated carpet showed no evidence of staining while an untreated control was deeply stained red. Carpets treated with the terpolymer alone did not yellow on 24 hour exposure to UV light.
- a bath of the stain resist solution is made up in a glass screw cap container.
- a typical application bath utilizes a 20 to 1 liquor to goods ratio with 1.0 weight % of stain resist active ingredient on weight of fiber.
- An alkyl aryl sulfonate (Alkanol® ND) or suitable leveling agent is also added at 15 % leveling agent on weight of stain resist active ingredient.
- the carpet piece (Dupont type 1150 Nylon 6,6 white; Superba heat set, mock dyed level loop carpet, 3/8 inch pile height, 30 ounces per yard, 1/10 inch gauge, 10 stitches per inch, woven polypropylene primary backing) is then fully immersed with the tuft side facing the center and no overlap.
- the required pH adjustment is then made.
- a pH of 2.0 is standard unless otherwise noted. All pH adjustments were accomplished utilizing an aqueous 30 % sulfamic acid solution.
- the jar is then capped and placed in a 70°C constant temperature water bath. The jar is removed after 40 minutes and the sample allowed to cool to room temperature. The carpet sample is removed, rinsed under running deionized water and squeezed dry by hand. The carpet thus prepared is then fully immersed in a screw cap jar containing 0.1 g of FD & C red dye # 40 per 1 liter of water. The jar is capped and the carpet allowed to stand in the solution for 24 hours. The carpet is removed and rinsed with tap water until no more stain is visually detectable in the rinse. The carpet is then dried in a 60xC oven and evaluated as described above.
- a terpolymer was prepared in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: MBIK (104.4 g) Styrene (4.1 g, 0.04 mol) Stilbene (10.8 g, 0.06 mol) Maleic Anhydride (9.8 g, 0110 mol) Dodecylmercaptan (1.4 g, 0.007 mol) Vazo® 67 (0.26 g, 0.0013 mol). Yield: 16.9 g
- the terpolymer was hydrolyzed in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (29.1 g) Aqueous NaOH, conc. 30% (10.9 g).
- a terpolymer was prepared in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: MIBK (101.6 g) Styrene (5.2 g, 0.05 mol) Stilbene (9.0 g, 0.05 mol) Maleic Anhydride (9.8 g, 0.10 mol) Dodecylmercaptan (1.4 g, 0.007 mol) VAZO® 67 (0.25 g, 0.0013 mol). Yield: 19.1 g
- the terpolymer was hydrolyzed in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (28.9 g) Aqueous NaOH, conc. 30% (11.1 g).
- a terpolymer was prepared in accordance with the procedure of Example 8, utilizing the following amounts of reactants and solvents: MIBK (98.4 g) Styrene (6.2 g, 0.06 mol) Stilbene (7.2 g, 0.04 mol) Maleic Anhydride (9.8 g, 0.10 mol) Dodecylmercaptan (1.4 g, 0.07 mol) VAZO® 67 (0.24 g, 0.0012 mol) Yield: 19.1 g
- the terpolymer was hydrolyzed in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (28.5 g) Aqueous NaOH, conc. 30% (11.5 g).
- a terpolymer was prepared in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: MIBK (92.4 g) Styrene (8.3 g, 0.08 mol) Stilbene (3.6 g, 0.02 mol) Maleic Anhydride (9.8 g, 0.10 mol) Dodecylmercaptan (1.4 g, 0.007 mol) VAZO® 67 (0.23 g, 0.0012 mol) Yield: 20.3 g
- the terpolymer was hydrolyzed in accordance with the procedure of Example 7, utilizng the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (28.2 g) Aqueous NaOH, conc. 30% (11.8 g).
- a terpolymer was prepared in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: MIBK (92.4 g) Styrene (8.3 g, 0.08 m0l) Stilbene (3.6 g, 0.02 mol) Maleic Anhdyride (9.8 g, 0.10 mol) Dodecylmercaptan (1.4 g, 0.007 mol) VAZO® 67 (0.23 g, 0.0012 mol) Yield: 20.3
- the terpolymer was hydrolyzed in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (27.7 g) Aqueous NaOH, conc. 30% (12.3 g).
- a terpolymer was prepared in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: MIBK (89.6 g) Styrene (9.4 g, 0.09 mol) Stilbene (1.8 g, 0.01 mol) Maleic Anhydride (9.8 g, 0.10 mol) Dodecylmercaptan (1.4 g, 0.007 mol) VAZO® 67 (0.21 g, 0.0011 mol) Yield: 19.6.g
- the terpolymer was hydrolyzed in accordance with the procedure of Example 7, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (27.3 g) Aqueous NaOH, conc. 30% (12.7 g).
- Methyl isobutyl ketone (1025 g) in a 4-neck 5.0 L flask fitted with mechanical agitation, condenser, temperature controller, nitrogen bubbler and heating mantle was heated to 70°C and sparged with nitrogen for one hour then cooled to room temperature.
- maleic anhydride 98.06 g, 1.0 mol
- 4-acetoxy stilbene 59.6 g, 0.25 mol
- styrene 78.11 g, 0.75 mol
- dodecylmercaptan 17.6 g, 0.087 mol
- VAZO® 67 initiator (2,2′-azobis-(2-methylbutyronitrile)] (2.3 g, 0.012 mol) was then added in one portion as a solid, no appreciable exotherm was noticed.
- the reaction was stirred at 70°C for 3 hours then additional VAZO® 67 (1.3 g, 0.067 mol) was added.
- the reaction was continued with stirring at 70°C for another 5 hours; then it was cooled to room temperature. Approximately 3/4 of the MIBK was then removed by rotary evaporation (or vacuum distillation at 10 mmHg).
- petroleum ether ca . 1 L
- the solid was collected by vacuum filtration and dried in a vacuum oven at 60°C to give the terpolymer as a light yellow powder 256 g, 100%).
- the product solution thus obtained was applied to nylon carpet at 5 percent on weight of fiber (1 percent active ingredient) in a simulated beck dyeing apparatus as described in EXAMPLE 7 at pH 2.0, 2.5, and 3.0.
- pH 2.0 there was no evidence of staining
- pH 2.5 showed a barely discernable pink stain
- pH 3.0 was noticeably stained
- carpets treated with the terpolymer alone did not yellow on 24 hour exposure to UV light.
- a terpolymer was prepared in accordance with the procedure of Example 15, utilizing the following amounts of reactants and solvents: MIBK (93.0 g) Styrene (9.37 g, 0.09 mol) 4-Acetoxy Stilbene (2.38 g, 0.01 mol) Maleic Anhydride (9.80 g, 0.10 mol) Dodecylmercaptan (1.61 g, 0.008 mol) VAZO® 67 (0.23 g, 0.0012 mol) Yield: 19.7.
- the terpolymer was hydrolyzed in accordance with the procedure of Example 15, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (28.7 g) Aqueous NaOH, conc. 30% (12.2 g) Yield: 48.7 g.
- a terpolymer was prepared in accordance with the procedure of Example 15, utilizing the following amounts of reactants and solvents: MIBK (146.0 g) Styrene (5.20 g, 0.05 mol) 4-Acetoxy Stilbene (11.9 g, 0.05 mol) Maleic Anhydride (9.80 g, 0.10 mol) Dodecylmercaptan (2.01 g, o.0015 mol) Yield: 24.6 g.
- the terpolymer was hydrolyzed in accordance with the procedure of Example 15, utilizing the following amounts of reactants and solvents: Terpolymer (10.0 g) Deionized water (26.2 g) Aqueous NaOH, conc. 30% (13.8 g) Yield: 47.7 g.
- Methylisobutylketone (MIBK - 100 mls) was heated to 70°C with a stream of nitrogen bubbling below the surface of the liquid for 2-1/2 hours. The nitrogen stream was then removed from below the surface. However, the system was kept under a nitrogen atmosphere. Maleic anhydride (9.8 g) was added along with 1.82 g of dodecylmercaptan, 14.5 g of styrene and 0.26 g of VAZO® 67 in that order. After heating for 3 hours at 75°C, an additional O.I3 g of VAZO® 67 was added and the reaction maintained at this temperature for 3 more hours. Yield of copolymer was 27.0 g.
- Example 20 was repeated except eugenol acetate was replaced with isoeugenol acetate. Yield of copolymer was 38.7 g.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Woven Fabrics (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Polyamides (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13603887A | 1987-12-21 | 1987-12-21 | |
US136038 | 1987-12-21 | ||
US28040788A | 1988-12-06 | 1988-12-06 | |
US280407 | 1988-12-06 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0329899A2 true EP0329899A2 (fr) | 1989-08-30 |
EP0329899A3 EP0329899A3 (en) | 1989-10-18 |
EP0329899B1 EP0329899B1 (fr) | 1994-12-28 |
Family
ID=26833934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88311835A Expired - Lifetime EP0329899B1 (fr) | 1987-12-21 | 1988-12-14 | Polymères aromatique/anhydride maléique résistant aux salissures |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0329899B1 (fr) |
JP (1) | JP2632990B2 (fr) |
KR (1) | KR920006476B1 (fr) |
AT (1) | ATE116389T1 (fr) |
AU (1) | AU617731B2 (fr) |
CA (1) | CA1332684C (fr) |
DE (1) | DE3852627T2 (fr) |
DK (1) | DK709888A (fr) |
FI (1) | FI885889A (fr) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0332342A2 (fr) * | 1988-03-11 | 1989-09-13 | Minnesota Mining And Manufacturing Company | Procédé pour rendre des matériaux polyamidiques résistants aux taches |
US4940757A (en) * | 1989-04-20 | 1990-07-10 | Peach State Labs, Inc. | Stain resistant polymeric composition |
WO1990012917A1 (fr) * | 1989-04-20 | 1990-11-01 | Peach State Labs, Inc. | Traitement antitaches pour fibres polyamides |
US5015259A (en) * | 1989-04-20 | 1991-05-14 | Peach State Labs, Inc. | Stain resistant polymeric composition |
WO1991014818A1 (fr) * | 1990-03-27 | 1991-10-03 | Allied-Signal Inc. | Methode pour conferer une resistance aux taches de cafe a des substrats de textile de polyamide |
WO1992007131A1 (fr) * | 1990-10-18 | 1992-04-30 | E.I. Du Pont De Nemours And Company | Polymeres aromatiques sulfones resistant aux taches |
US5118551A (en) * | 1990-03-27 | 1992-06-02 | Allied-Signal Inc. | Method to impart stain resistance to polyamide textile substrates |
WO1992010605A1 (fr) * | 1990-12-13 | 1992-06-25 | E.I. Du Pont De Nemours And Company | Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique |
WO1992012286A1 (fr) * | 1990-12-27 | 1992-07-23 | E.I. Du Pont De Nemours And Company | Matieres resistant aux taches a base de polymeres d'allylether ou de vinylether/d'anhydride maleique |
WO1992013989A1 (fr) * | 1991-02-01 | 1992-08-20 | Allied-Signal Inc. | Procede et composition ameliorant la resistance de polyamides aux taches de colorant acide |
WO1993001348A1 (fr) * | 1991-07-10 | 1993-01-21 | Minnesota Mining And Manufacturing Company | Compositions de traitement fluorochimique impermeables a l'eau et a l'huile |
US5223340A (en) * | 1989-04-20 | 1993-06-29 | Peach State Labs, Inc. | Stain resistant polyamide fibers |
US5232760A (en) * | 1991-02-01 | 1993-08-03 | Allied Signal Inc. | Method and composition to enhance acid dye stain resistance of polyamides by improving resistance to detergent washings and products thereof |
US5236464A (en) * | 1991-12-16 | 1993-08-17 | Allied-Signal Inc. | Activation of nylon fibers for modification by UV radiation |
WO1993019238A1 (fr) * | 1992-03-25 | 1993-09-30 | E.I. Du Pont De Nemours And Company | Revetements antitaches pour substrats de polyamide |
US5252232A (en) * | 1991-09-20 | 1993-10-12 | E. I. Du Pont De Nemours And Company | Stain and soil resistant compositions having freeze-thaw stability |
US5310828A (en) * | 1989-04-20 | 1994-05-10 | Peach State Labs, Inc. | Superior stain resistant compositions |
WO1994018376A1 (fr) * | 1993-02-02 | 1994-08-18 | E.I. Du Pont De Nemours And Company | Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable |
US5520962A (en) * | 1995-02-13 | 1996-05-28 | Shaw Industries, Inc. | Method and composition for increasing repellency on carpet and carpet yarn |
WO1997031149A1 (fr) * | 1996-02-23 | 1997-08-28 | E.I. Du Pont De Nemours And Company | Agents antitaches a resine de resol/polymeres contenant de l'acide carboxylique |
WO1997033926A1 (fr) * | 1996-03-13 | 1997-09-18 | E.I. Du Pont De Nemours And Company | Copolymeres d'acide maleique proteges par un thiether fluore |
US5834088A (en) * | 1990-12-13 | 1998-11-10 | E. I. Du Pont De Nemours And Company | Maleic anhydride/olefin polymer stain-resists |
FR2805288A1 (fr) * | 2000-02-23 | 2001-08-24 | Atofina | Composition pour le traitement anti-taches et anti- salissures des moquettes et procede de traitement correspondant |
US7335234B2 (en) | 2002-10-16 | 2008-02-26 | Columbia Insurance Company | Method of treating fibers, carpet yarns and carpets to enhance repellency |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU615242B2 (en) * | 1987-12-21 | 1991-09-26 | E.I. Du Pont De Nemours And Company | Stain-resistant agents for textiles |
US6524492B2 (en) | 2000-12-28 | 2003-02-25 | Peach State Labs, Inc. | Composition and method for increasing water and oil repellency of textiles and carpet |
JP6213132B2 (ja) * | 2013-10-11 | 2017-10-18 | 東ソー株式会社 | trans−スチルベン−無水マレイン酸共重合体及びそれを用いた位相差フィルム |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835071A (en) * | 1969-11-17 | 1974-09-10 | Atlantic Richfield Co | Rug shampoo compositions |
FR2240978A1 (en) * | 1973-08-13 | 1975-03-14 | Hoechst Ag | Treating cellulose or mixed cellulose fabrics - in alkaline baths contg. wetting agents and maleic acid copolymer, giving better bleaching |
FR2357681A1 (fr) * | 1976-07-06 | 1978-02-03 | Ciba Geigy Ag | Procede pour appliquer des apprets a la fois anti-statiques et anti-salissure a des matieres textiles synthetiques |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5319492A (en) * | 1976-08-02 | 1978-02-22 | Kao Corp | Size agent component |
-
1988
- 1988-12-12 KR KR1019880016606A patent/KR920006476B1/ko not_active IP Right Cessation
- 1988-12-14 DE DE3852627T patent/DE3852627T2/de not_active Expired - Lifetime
- 1988-12-14 AT AT88311835T patent/ATE116389T1/de not_active IP Right Cessation
- 1988-12-14 EP EP88311835A patent/EP0329899B1/fr not_active Expired - Lifetime
- 1988-12-15 CA CA000586056A patent/CA1332684C/fr not_active Expired - Lifetime
- 1988-12-20 FI FI885889A patent/FI885889A/fi not_active Application Discontinuation
- 1988-12-20 DK DK709888A patent/DK709888A/da not_active Application Discontinuation
- 1988-12-20 AU AU27089/88A patent/AU617731B2/en not_active Expired
- 1988-12-21 JP JP63323212A patent/JP2632990B2/ja not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835071A (en) * | 1969-11-17 | 1974-09-10 | Atlantic Richfield Co | Rug shampoo compositions |
FR2240978A1 (en) * | 1973-08-13 | 1975-03-14 | Hoechst Ag | Treating cellulose or mixed cellulose fabrics - in alkaline baths contg. wetting agents and maleic acid copolymer, giving better bleaching |
FR2357681A1 (fr) * | 1976-07-06 | 1978-02-03 | Ciba Geigy Ag | Procede pour appliquer des apprets a la fois anti-statiques et anti-salissure a des matieres textiles synthetiques |
Cited By (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0332342A3 (fr) * | 1988-03-11 | 1991-09-18 | Minnesota Mining And Manufacturing Company | Procédé pour rendre des matériaux polyamidiques résistants aux taches |
EP0332342A2 (fr) * | 1988-03-11 | 1989-09-13 | Minnesota Mining And Manufacturing Company | Procédé pour rendre des matériaux polyamidiques résistants aux taches |
EP0428639A1 (fr) * | 1989-04-20 | 1991-05-29 | Peach State Labs Inc | Traitement antitaches pour fibres polyamides. |
US5061763A (en) * | 1989-04-20 | 1991-10-29 | Peach State Labs, Inc. | Stain resistant treatment for polyamide fibers |
US5223340A (en) * | 1989-04-20 | 1993-06-29 | Peach State Labs, Inc. | Stain resistant polyamide fibers |
WO1990012917A1 (fr) * | 1989-04-20 | 1990-11-01 | Peach State Labs, Inc. | Traitement antitaches pour fibres polyamides |
GR900100293A (el) * | 1989-04-20 | 1991-09-27 | Peach State Labs Inc | Κατεργασια δημιουργιας αντοχης εναντι των κηλιδων για ινες πολυαμιδης. |
EP0428639A4 (en) * | 1989-04-20 | 1991-10-02 | Peach State Labs, Inc. | Stain resistant treatment for polyamide fibers |
US5310828A (en) * | 1989-04-20 | 1994-05-10 | Peach State Labs, Inc. | Superior stain resistant compositions |
US5015259A (en) * | 1989-04-20 | 1991-05-14 | Peach State Labs, Inc. | Stain resistant polymeric composition |
US4940757A (en) * | 1989-04-20 | 1990-07-10 | Peach State Labs, Inc. | Stain resistant polymeric composition |
US5118551A (en) * | 1990-03-27 | 1992-06-02 | Allied-Signal Inc. | Method to impart stain resistance to polyamide textile substrates |
US5364541A (en) * | 1990-03-27 | 1994-11-15 | Calcaterra Lidia T | Method to impart coffee stain resistance to polyamide textile substrates |
US5135774A (en) * | 1990-03-27 | 1992-08-04 | Allied-Signal Inc. | Method to impart coffee stain resistance to polyamide fibers |
US5359010A (en) * | 1990-03-27 | 1994-10-25 | Alliedsignal Inc. | Method to impart coffee stain resistant to polyamide textile substances |
WO1991014818A1 (fr) * | 1990-03-27 | 1991-10-03 | Allied-Signal Inc. | Methode pour conferer une resistance aux taches de cafe a des substrats de textile de polyamide |
WO1992007131A1 (fr) * | 1990-10-18 | 1992-04-30 | E.I. Du Pont De Nemours And Company | Polymeres aromatiques sulfones resistant aux taches |
EP0648886A3 (fr) * | 1990-12-13 | 1996-05-15 | Du Pont | Agents antitâches contenant des polymères d'anhydride maléique/oléfine. |
US5834088A (en) * | 1990-12-13 | 1998-11-10 | E. I. Du Pont De Nemours And Company | Maleic anhydride/olefin polymer stain-resists |
WO1992010605A1 (fr) * | 1990-12-13 | 1992-06-25 | E.I. Du Pont De Nemours And Company | Agents anti-taches contenant des polymeres d'olefine/d'anhydride maleique |
AU660639B2 (en) * | 1990-12-13 | 1995-07-06 | E.I. Du Pont De Nemours And Company | Maleic anhydride/olefin polymer stain-resists |
WO1992012286A1 (fr) * | 1990-12-27 | 1992-07-23 | E.I. Du Pont De Nemours And Company | Matieres resistant aux taches a base de polymeres d'allylether ou de vinylether/d'anhydride maleique |
US5348786A (en) * | 1991-02-01 | 1994-09-20 | Allied-Signal Inc. | Method and composition to enhance acid dye stain resistance of polyamides by improving resistance to detergent washings and products thereof |
US5232760A (en) * | 1991-02-01 | 1993-08-03 | Allied Signal Inc. | Method and composition to enhance acid dye stain resistance of polyamides by improving resistance to detergent washings and products thereof |
WO1992013989A1 (fr) * | 1991-02-01 | 1992-08-20 | Allied-Signal Inc. | Procede et composition ameliorant la resistance de polyamides aux taches de colorant acide |
WO1993001348A1 (fr) * | 1991-07-10 | 1993-01-21 | Minnesota Mining And Manufacturing Company | Compositions de traitement fluorochimique impermeables a l'eau et a l'huile |
AU653629B2 (en) * | 1991-07-10 | 1994-10-06 | Minnesota Mining And Manufacturing Company | Fluorochemical water- and oil- repellent treating compositions |
US5370919A (en) * | 1991-07-10 | 1994-12-06 | Minnesota Mining And Manufacturing Company | Fluorochemical water- and oil-repellant treating compositions |
US5252232A (en) * | 1991-09-20 | 1993-10-12 | E. I. Du Pont De Nemours And Company | Stain and soil resistant compositions having freeze-thaw stability |
US5236464A (en) * | 1991-12-16 | 1993-08-17 | Allied-Signal Inc. | Activation of nylon fibers for modification by UV radiation |
WO1993019238A1 (fr) * | 1992-03-25 | 1993-09-30 | E.I. Du Pont De Nemours And Company | Revetements antitaches pour substrats de polyamide |
WO1994018376A1 (fr) * | 1993-02-02 | 1994-08-18 | E.I. Du Pont De Nemours And Company | Composition anti-tache a base de polymere anhydride maleique hydrolyse et durable |
US5520962A (en) * | 1995-02-13 | 1996-05-28 | Shaw Industries, Inc. | Method and composition for increasing repellency on carpet and carpet yarn |
WO1997031149A1 (fr) * | 1996-02-23 | 1997-08-28 | E.I. Du Pont De Nemours And Company | Agents antitaches a resine de resol/polymeres contenant de l'acide carboxylique |
US5708087A (en) * | 1996-02-23 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Carboxylic acid-containing polymer/resole stain-resists |
WO1997033926A1 (fr) * | 1996-03-13 | 1997-09-18 | E.I. Du Pont De Nemours And Company | Copolymeres d'acide maleique proteges par un thiether fluore |
US5712348A (en) * | 1996-03-13 | 1998-01-27 | E. I. Du Pont De Nemours And Company | Maleic acid copolymers with fluorinated thioether end-cap |
US5824372A (en) * | 1996-03-13 | 1998-10-20 | E. I. Du Pont De Nemours And Company | Maleic acid copolymers with fluorinated thioether end cap |
FR2805288A1 (fr) * | 2000-02-23 | 2001-08-24 | Atofina | Composition pour le traitement anti-taches et anti- salissures des moquettes et procede de traitement correspondant |
US7335234B2 (en) | 2002-10-16 | 2008-02-26 | Columbia Insurance Company | Method of treating fibers, carpet yarns and carpets to enhance repellency |
Also Published As
Publication number | Publication date |
---|---|
DK709888A (da) | 1989-06-22 |
DE3852627D1 (de) | 1995-02-09 |
JPH02138365A (ja) | 1990-05-28 |
FI885889A (fi) | 1989-06-22 |
AU2708988A (en) | 1989-06-15 |
JP2632990B2 (ja) | 1997-07-23 |
CA1332684C (fr) | 1994-10-25 |
AU617731B2 (en) | 1991-12-05 |
ATE116389T1 (de) | 1995-01-15 |
DK709888D0 (da) | 1988-12-20 |
KR890010353A (ko) | 1989-08-08 |
EP0329899B1 (fr) | 1994-12-28 |
KR920006476B1 (ko) | 1992-08-07 |
EP0329899A3 (en) | 1989-10-18 |
DE3852627T2 (de) | 1995-06-08 |
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