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WO2001021677A1 - Systeme d'amorçage a radicaux libres et procede de polymerisation d'acides ethyleniques dicarboxyliques - Google Patents

Systeme d'amorçage a radicaux libres et procede de polymerisation d'acides ethyleniques dicarboxyliques Download PDF

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Publication number
WO2001021677A1
WO2001021677A1 PCT/US2000/040990 US0040990W WO0121677A1 WO 2001021677 A1 WO2001021677 A1 WO 2001021677A1 US 0040990 W US0040990 W US 0040990W WO 0121677 A1 WO0121677 A1 WO 0121677A1
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total weight
concentration
free radical
acid
reducing agent
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PCT/US2000/040990
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English (en)
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Charles Q. Yang
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University Of Georgia Research Foundation, Inc.
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Priority to AU14922/01A priority Critical patent/AU1492201A/en
Publication of WO2001021677A1 publication Critical patent/WO2001021677A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid

Definitions

  • Polycarboxylic acids are useful in many fields. For example, in the fabric treatment field, polycarboxylic acids are promising nonformaldehyde durable press finishing agents for cotton to replace the traditional N-methylol reagents (Laemmermann, D. (1992), "New
  • Multifunctional acids have also been used as crosslinking agents to improve paper wet strength (Caulifield, D.F. (1994), "Crosslinking to Improve wet performance of Paper Using Multifunctional Carboxylic Acids,
  • Butanetetracarboxylic Acid and Citric Acid Tappi J. 77(3):204-212; Horie, D. and Biermann, C.J. (1994), “Applications of Durable Press Treatment to Bleached Softwood Kraft Handsheets,” Tappi J. 77(8):135-140; Yang, C.Q. and Xu, Y. (1998), “Paper Wet Performance and Ester Crosslinking of Wood Pulp Cellulose by the Polycarboxylic Acids," J. Appl. Polym. Sci. 67:649-658; Zhou, Y.J. et al. (1993), "Reinforcing of Paper and Board by
  • Novel Crosslinking Chemicals Prod. Papermaking 2:1045-1072.
  • Maleic acid (MA), fumaric acid (FA), itaconic acid (IA) and other olefinically unsaturated compounds containing at least two carbonyl groups are historically extremely difficult to homopolymerize in their acidic forms in comparison to mono substituted ethylenical acid monomers such as acrylic acid.
  • PMA Poly(maleic acid)
  • MAN polymerizing maleic anhydride
  • PMAN poly(maleic anhydride)
  • benzoyl peroxide followed by hydrolysis of PMAN to form PMA
  • MA was reported to form a polymer complex with polyvinylpyrrolidone in water using potassium persulfate (Sato, T. et al. (1979), "Radical Polymerization of Maleic Acid by Potassium Persulfate in the Presence of Polyvinylpyrrolidone in Water,” J. Macromol. Sci. Chem. A13(6):751-766).
  • Polymaleate was reported to be prepared using monosodium, monopotassium or monoammonium malate in aqueous solutions in the presence of sodium hydroxide, potassium hydroxide or ammonia and certain initiators under specialized conditions (U.S. Patent 4,668,735; U.S. Patent No. 4,709,091), or using a catalyst such as hydrogen peroxide and a vanadium, iron or copper ion (U.S. Patent No. 5,064,563) or a metal salt such as iron sulfate heptahydrate as a "promoter" in combination with a water soluble initiator (U.S. Patent No.
  • I A is easier to polymerize than MA and FA because of the 1,1-disubstitution structure of IA rather than the 1 ,2-disubstitution structure of MA and FA.
  • Homopolymerization of IA was reported in 1959. This polymerization was carried out in a 0.5 N hydrochloric acid solution with K 2 S 2 O 8 as an initiator and took several days to complete. The conversion of IA to poly(itaconic acid) (PIA) was reported to be only 35% (Marvel, C.S. and Shepherd, T.H. (1959), "Polymerization Reaction of Itaconic Acid and Some of Its Derivatives," J. Org. Chem. 24:599-605).
  • IA was also reported to be polymerized in selected solvents under high pressure (5000Kg/cm 2 ).
  • PIA was reported to be synthesized in methanol at room temperature with AIBN as a free-radical initiator, but the polymerization took 30 days to complete with a 70% yield (Vellckovic, J. et al. (1994), "The Synthesis and Characterization of Poly(Itaconic acid),” Polym. Bull. 32:169-170).
  • PIA has been reported to be made in water in the presence of ferric ammonium sulfate, hydrogen peroxide and NaOH (U.S. Patent No. 5,336,744).
  • a polymerization initiation system comprising a free radical generator and a phosphorous-containing reducing agent is provided.
  • the free radical generator is present at a concentration of between about 1 to about 4% of the total weight of the system, including between about 2 to about 4% of the total weight of the system, between about 1 to about 3% of the total weight of the system, and between about 2 to about 3.5% of the total weight of the system.
  • the reducing agent is present at a concentration of between about 1 to about 25% of the total weight of the system, including between about 1 to about 10% of the total weight of the system, between about 1 to about 15% of the total weight of the system, and between about 1 to about 5% of the total weight of the system.
  • the ranges given for the free radical generator and reducing agent include all intermediate ranges other than those specifically described herein.
  • the mole ratio of the free radical generator reducing agent is between about 0.1 :10 to about 10:0.1, including all intermediate ranges therein, preferably between about 0.1 :1 to about 1 :1.
  • An aqueous solvent is preferred, with water being most preferred.
  • the system can also be used in an emulsion.
  • This polymerization system can be used to polymerize olefinically unsaturated compounds with at least two carboxyl groups.
  • the polymerization system may be used to polymerize other vinyl monomers, as well.
  • Homopolymers and copolymers may be prepared using the method provided herein.
  • the system may also include an emulsifier at a concentration of between about 0.05 to about 0.5% of the total weight of the system, including all intermediate ranges therein. This method can be used to form polymers and copolymers on cellulose substrates, such as fabrics and nonwovens.
  • a preferred embodiment of the system is a method of polymerizing at least one olefinically unsaturated compound containing at least two carboxyl groups, such as maleic acid (cis-l,2-ethylenedicarboxylic acid, MA), fumaric acid (trans- 1 ,2-ethylenedicarboxylic acid, FA), itaconic acid (l,2-propene-3-dicarboxylic acid, IA), citraconic acid, cis-aconitic acid, trans-aconitic acid and 3-butene-l,2,3-tricarboxylic acid, which comprises: (a) mixing a phosphorous-containing reducing agent, one or more olefinically unsaturated monomers which contain at least two carboxyl groups, and a free radical generator to form a mixture; and (b) subjecting said mixture to polymerization conditions.
  • olefinically unsaturated compound containing at least two carboxyl groups such as maleic acid (cis-l,2-ethylenedicarboxylic acid, MA
  • the monomer or mixture of monomers may be present in the mixture at a concentration of between about 1 and about 50%) of the total weight of the mixture and all intermediate ranges therein, including between about 1 to about 25% of the total weight of the mixture, between about 10-40% of the total weight of the mixture and between about 25-50%) of the total weight of the mixture.
  • the reducing agent may be present in the mixture at a concentration of between about 1 and about 25%) of the total weight of the mixture and all intermediate ranges therein, preferably between about 1 and about 15%) of the total weight of the mixture and those ranges specifically listed above.
  • the mole ratio of the free radical generator reducing agent is between about 0.1 : 10 to about 10:0.1 and all intermediate ranges therein. It is preferred that the mole ratio of the free radical generator:reducing agent be between about 0.1 :1 to about 1 :1.
  • Another preferred embodiment of the polymerization system is a method of forming polymers on cellulose substrates, such as fabrics and nonwovens comprising: (a) immersing a substrate in a solution comprising at least one monomer that contains at least two carboxyl groups at a monomer concentration of between about 2 and about 15 % of the total weight of solution, said solution also comprising a free radical generator at a concentration of between about 1 and about 4 % of the total weight of solution and a phosphorous-containing reducing agent at a concentration of between about 1 and about 10 % of the total weight of solution; and (b) curing the substrate.
  • Polymers and copolymers may be produced in-situ on cellulose substrates, including fabrics and nonwovens, preferably cotton fabric, by this method.
  • Polymers and copolymers may be produced on other fabrics as well, such as rayon and cotton-polyester blends.
  • Preferred copolymers include MA and I A.
  • the preferred ratio of MA to I A is between about 1 : 1 to about 4:1.
  • All ranges given for the monomers, free radical generators and reducing agents and other components include all intermediate ranges therein, including those specifically listed herein. It is preferred that the free radical generator be present at a concentration of about 2%> of the total weight of solution. It is preferred that the reducing agent be present at a concentration of about 4% of the total weight of solution.
  • the system may also include an emulsifier at a concentration of between about 0.05 to about 0.5% of the total weight of the system.
  • a polymerization system comprising: a free radical generator at a concentration of between about 1 to about 4%> of the total weight of the system and a phosphorous-containing reducing agent at a concentration of between about 1 to about 25%) of the total weight of the system and an aqueous solvent.
  • the free radical generator is preferably selected from the group consisting of: Na 2 S 2 O 8 , K 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8 and H 2 O 2 at a concentration of above about 2% of the total weight of the system.
  • the reducing agent is preferably selected from the group consisting of: NaH 2 PO 2 and Na 2 HPO 3 at a concentration of between about 1 to 10%) of the total weight of the system.
  • the mole ratio of said free radical generator:phosphorous-containing reducing agent is preferably between about 0.1 :10 to about 10:0.1.
  • This system may further comprise one or more olefinically unsaturated compounds containing at least two carboxyl groups at a concentration of between about 1 to about 50%) of the total weight of the system, and all intermediate ranges therein, including those specifically listed herein.
  • “Curing” the substrate involves subjecting the substrate to a temperature of between about 150 and about 200 °C, as known in the art. Preferably a temperature of about 180°C is used to cure the substrate.
  • the substrate may be dried after immersion in the polymerization solution and before curing. Drying may occur at any suitable temperature, preferably about 70 to 100°C, as is known in the art.
  • Substrates include cellulose substrates such as fabric and nonwovens. Cotton fabric is a preferred substrate.
  • the polymerization method for ethylenical dicarboxylic acids such as MA, FA and IA described uses those acids in their acidic forms and the temperature range normally used for aqueous free radical polymerization (about 60-100 °C) without any "promoters" other than the reduction-oxidation initiation system itself. It can achieve >95%> monomer conversion within a relatively short period of time (for example, about 1 hr).
  • PMA synthesized with this method has significantly lower monomer content than the commercially available PMA, which is produced by polymerizing MAN followed by alkaline hydrolysis of PMAN.
  • free radical generator takes its usual meaning in the art and is also referred to as an initiator.
  • free radical generators include salts of persulfates such as Na 2 S 2 O 8 , K 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8 and water soluble peroxides such as hydrogen peroxide. Free radical generators used herein are water soluble.
  • reducing agent takes its usual meaning in the art and includes those substances that donate electrons to another species.
  • Reducing agents useful in the invention are those that contain phosphorous, including, but not limited to NaH 2 PO 2 and Na 2 HPO 3 .
  • polymerization conditions include those under which polymerization can occur.
  • Polymerization conditions include a temperature of between about 40 and about 100 °C and all intermediate ranges therein, including from about 40 to about 80 °C and from between about 50 to about 85 °C
  • the polymerization typically takes between about five minutes to about six hours to produce the desired degree of polymerization.
  • Preferred polymerization conditions include a temperature of between about 60 to about 100 °C and a time of between about thirty minutes to about four hours.
  • mixing reaction components with each other refers to providing a medium and/or reaction chamber in which the reaction components are placed together so that they can react with each other.
  • the reaction components are suspended or dissolved in a solvent which is a liquid medium. More preferably, an aqueous solution is used as the solvent. Most preferably, water is used as the solvent.
  • an emulsion may be used where an emulsifier such as sodium dodecyl sulfate is used and insoluble monomers such as esters of maleic acid, fumaric acid or itaconic acid are polymerized.
  • a mixture of water, emulsifier, monomer, free radical generator and reducing agent is used. When emulsions are used, the concentration of components can be higher than when components are dissolved in a solvent.
  • a "mixture" of compounds is not meant to imply that the compounds necessarily form a completely soluble solution. Mixture merely means that the compounds contact each other.
  • the compounds forming the mixture may be completely or partially soluble in the solvent or may form an emulsion.
  • Olefinically unsaturated compounds which contain at least two carboxyl groups include those compounds where the carbon-carbon double bond is a terminal group of the compound, such as IA and those compounds where the carbon-carbon double bond is positioned within the carbon chain of the backbone, such as MA and FA.
  • the methods of the invention are useful to polymerize ethylenical dicarboxylic acids other than those specifically illustrated.
  • Olefinically unsaturated compounds which contain at least two carboxyl groups are also referred to as ethylenical dicarboxylic acids.
  • the olefinically unsaturated compounds useful in the invention may contain more than one double bond.
  • olefinically unsaturated compounds which contain only one carboxyl group may be polymerized using the method of the invention.
  • Copolymers may be prepared using the method of the invention using one or more olefinically unsaturated compounds which contain at least two carboxyl group and one or more olefinically unsaturated compounds which contain only one carboxyl group, such as methacrylic acid.
  • copolymers are also prepared by the method of the invention.
  • Such copolymers include, but are not limited to copolymers formed from the polymerization of MA and IA and copolymers formed from the polymerization of fumaric acid, maleic acid or itaconic acid with a second monomer.
  • Copolymers may be formed from an ethylenical dicarboxylic acid and a vinyl monomer.
  • one or more of the ethylenical dicarboxylic acids e.g., MA, FA, and IA
  • the reducing agent e.g., NaH 2 PO 2
  • the monomer concentration is about 1 - 50% depending on the solubility of the monomer.
  • the concentration of the reducing agent is from about 1 to about 25%, preferably about 2 - 10%).
  • the mixture is heated to desired temperatures ranging from about 40 - 100°C, preferably from about 60 to 100°C
  • the heat may be applied before, after or during the addition of the free radical generator and reducing agent.
  • the free radical initiator e.g., K 2 S 2 O 8
  • the whole amount of the free radical initiator can be added at one time, or portions of the free radical initiator can be added batchwise during the polymerization process. A portion of the total amount of free radical initiator used can be added to the mixture before applying heat and a portion of the total amount of free radical initiator can be added to the mixture after applying heat.
  • the mole ratio of the free radical initiator/monomers is from about 0.1 :10 to 2:10, preferably 0.5:10 to 1 :10.
  • the mole ratio of the free radical initiator/reducing agent is from about 0.1 :10 to about 10:0.1, preferably from about 0.2:1 to about 2:1.
  • N 2 may be used to purge the polymerization system.
  • the polymerization time is typically from about 5 mins to about 6 hr, preferably from about 30 mins to about 2 hr.
  • the polymerization process can be carried out in aqueous solutions as solution polymerization or in emulsions as emulsion polymerization.
  • an emulsifier is used, and monomers, such as esters of MA, FA and I A, insoluble in water are polymerized.
  • the polymers of olefinically unsaturated compounds produced by this method can be used as durable press finishing agents for fabrics, scale inhibitors for water treatment, and incrustation inhibitors in detergents, among other uses.
  • FIGURES Figure 1 Raman spectra of 6%> K 2 S 2 O 8 : (A) before heating; (B) heated at 50°C for 120 min; (C) heated at 100° C for 10 min; and (D) Raman spectrum of 6% K 2 SO 2 without heating.
  • Figure 2 Raman spectrum of (A) the aqueous solution of 10%> NaH 2 PO 2 ; (B) the mixture of 4.7% NaH 2 PO 2 and 6% K 2 S 2 O g at 65 °C; (C) the mixture of 4.7% NaH 2 PO 2 and 6% K 2 S 2 O 8 heated at 65 °C for 10 min; and (D) the mixture of 4.7% NaH 2 PO 2 and 6% K 2 S 2 O 8 heated at 65 °C for 20 min.
  • Figure 3 Raman spectra of the mixture of 25%) MA and 10% NaH 2 PO 2 (A) before heating; (B) instantly after the first % of 3.1% K 2 S 2 0 8 was added at 90°C; (C) after the second '/. of 3.1%> K 2 S 2 O 8 was added when the mixture was kept at 90 °C for 10 min; (D) after the third l ⁇ of 3.1%> K 2 S 2 O 8 was added when the mixture was kept at 90 °C for 20 min; (E) after the fourth ! ⁇ of 3.1% K 2 S 2 O 8 was added when the mixture was kept at 90°C for 30 min; and (F) when the mixture was kept at 90 °C for total of 75 min.
  • Figure 5 Cumulative weight fraction versus molar mass of PMA.
  • Figure 6 The Raman spectra of (A) the mixture of 0.7% FA and 10% NaH 2 PO 2 , (B) the mixture of 18.6%) FA. 10%) NaH 2 PO 2 and 2.5% K 2 S 2 O 8 kept at 95 °C for 5 min; and (C) the mixture of 18.6% FA, 10% NaH 2 PO 2 and 2.5% K 2 S 2 O 8 first kept at 95 °C for 10 min, then at 82°C for 30 min.
  • Figure 7 The Raman spectra of the mixture 243% IA and 8.6% NaH 2 PO 2 : (A) when the temperature was increased to 95 °C; (B) when the first Vz of 2.9%> K 2 S 2 O 8 was added, then the mixture was kept at 95 °C for 10 min; (C) when the second V_ of 2.9% K 2 S 2 O 8 was added and the mixture was kept at 95 °C for another 10 min; (D) when the third Vb of 2.9%> K 2 S 2 0 8 was added and the mixture was kept at 95 °C for another 10 min; and (E) when the mixture was kept at 95 °C for total of 60 min.
  • Figure 8 Infrared spectra of (A) cotton treated with 6.0% MA and dried at 80 °C, (B) cotton thus treated and cured at 180° C for 2 minutes, and (C) difference spectrum, B-A.
  • Figure 9 Infrared spectra of (A) cotton treated with 6.7% IA and dried at 80°C, (B) cotton thus treated and cured at 200 °C for 2 minutes, and (C) difference spectrum, B-A.
  • Figure 11 Difference spectra of cotton treated with 6.7% IA and 4.0% NaH 2 PO 2 in combination with different concentrations of K 2 S 2 O 8 (0.00,0.25, 0.50, 1.00, and 2.00%, A-E) before and after curing at 180°C for 2 minutes.
  • Figure 12 CIE whiteness index of cotton treated with 6.7% IA and 4% NaH 2 PO 2 in combination with different concentrations of K 2 S 2 O 8 and cured at 180° C for 2 minutes.
  • Figure 13 Percentage of free monomers (w/w) of cotton treated with 6% MA, 6.1% IA, and 4% NaH 2 PO 2 in combination with different concentrations of K 2 S 2 O 8 and cured at 180°C for 2 minutes.
  • Figure 14 Infrared spectra of (A) cotton treated with 6.7%> IA, 4.0%> NaH 2 PO 2 , and 2.0%) K 2 S 2 O 8 , cured at 180°C for 2 minutes, subjected to ten washing cycles, treated with acetic acid, (B) cotton thus treated and then cured at 180°C for 2 minutes, (C) difference spectrum, B-A.
  • FT-Raman Spectroscopic Measurements Nicolet 950 FT-Raman spectrometer with a liquid sample accessory and an InGaAs detector was used to collect all the Raman spectra.
  • the resolution was 8 cm "1 and there were 100 scans for each spectrum. No baseline correction or smoothing functions were used to process the data.
  • MALDI Matrix-assisted Laser desorption and ionization
  • TOF time-of-flight
  • the GPC data were collected and processed by ASTRA 4.70 software (Wyatt Technology).
  • a 0.5M aqueous NaNO 3 solution with a flow rate of 0.8 ml/min was used as a mobile phase at room temperature.
  • the injection volume was 20 ⁇ l.
  • the light scattering photometer was equipped with a laser at 633nm. It was calibrated using toluene, and the Rayleigh ratio was determined to be 1.406xl0 5 cm _1 . Normalization was carried out using a standard polyethylene oxide sample with molecular weight of 23,000.
  • the differential refractive index increment (dn/dc) of PMA in 0.5M NaNO 3 was 0.144ml/g as reported in the literature (J. Groot, J.G. Hollander, J. Bleijser, Macromolecules, 30, 6884 (1997)).
  • the cotton fabric was a desized and bleached plain weave 100% cotton fabric (Testfabrics Style 400).
  • the polyethylene softener was an industrial product made by Sequa, Chester, South Carolina
  • a cotton fabric sample was first immersed in an aqueous solution containing the desired chemicals.
  • the treated fabric sample was passed through a two-roll laboratory padder made by Rapid Labortex though two dips and two nips, and dried at 80 °C for 3 min. The wet pick-up was in the range of 95-100%).
  • the fabric was then cured in a Mathis curing oven at a specified temperature. All the concentrations are presented as %> weight of bath (wob).
  • the fabric properties measured and the standard methods used are presented in Table 1.
  • the fabric properties were evaluated after one home laundering washing/drying cycle without a detergent.
  • the performance of the finished fabric was also evaluated after different numbers of home laundering washing/drying cycles.
  • the home laundering washing process was conducted according to AATCC standard method 124-1992.
  • the fabric CIE whiteness index (WI) was measured before washing using LabScan 6000 spectrocolorimeter made by Hunter Associates Laboratory.
  • Wiley mill to form a powder before analysis.
  • a NaOH solution was added to the powder to convert the unsaturated carboxylic acids to their sodium salts, followed by the addition of a saturated NaBr methanol solution with excess NaBr.
  • Quantitative addition reaction of the unsaturated carboxylic acids by Br 2 takes place when a standard Br 2 /NaBr aqueous solution was added to the mixture.
  • the quantity of the excess amount of Br 2 was then determined by iodometric titration.
  • the percentage of the remaining free monomers (e.g., MA and IA) on fabric was calculated by the quantity of Br 2 consumed and the equation described as follows: [(no. of mmoles of Br 2 consumed by one gram of the fabric after curing) ⁇ (no. of mmoles of Br 2 consumed by one gram of the fabric before curing)]x 100%.
  • Shown in Figure 2 A is the Raman spectrum of the aqueous solution of 10% NaH 2 PO 2 .
  • a weak band at 980 cm “1 due to SO 4 2" appears in the Raman spectrum when 4.1% NaH 2 PO 2 is added to an aqueous solution of 6%> K 2 S 2 O 8 ( Figure 2B).
  • the bands at 980 cm “1 due to SO 4 2” becomes stronger and the two bands at 1075 and 835 cm “1 due to S 2 O 8 2" become weaker when the aqueous solution of 6.0%) K 2 S 2 O 8 and 4.7%NaH 2 PO 2 is heated at 65°C for 10 min ( Figure 2C).
  • the data indicate that a reduction-oxidation reaction between K 2 S 2 O 8 and NaH 2 PO 2 shown below takes places and the free radicals are formed as a result of the decomposition of S 2 O 8 2" .
  • the PMA synthesized was also studied with MALDI/TOF mass spectroscopy.
  • the assignment of the mass peaks is summarized in Table 3.
  • FIG. 4A and 4B are the GPC chromatograms of PMA with refractive index (RI) detector and the light scattering (LS) detector at 90°, respectively.
  • Figure 5 shows the curve of cumulative weight fraction as a function of the molar mass for PMA.
  • M w weight average molecular weight
  • M n number average molecular weight
  • the polydispersity of the molecular weight (M w /M n ) is 1.95. Based on the FT-Raman spectroscopy and the GPC -MALLS data, MA was believed to homopolymerize in the presence of the NaH 2 PO 2 /K 2 S 2 O g initiation system.
  • IA/NaH 2 PO 2 mixture is presented in Figure 7A.
  • K 2 S 2 O g by total weight of the final mixture was added to the IA/NaH 2 PO 2 mixture as soon as the temperature reaches 95 °C.
  • the intensities of the bands at 3117, 3007 and 1642 cm" 1 due to IA are significantly reduced 10 min after the addition of K 2 S,O g ( Figure 7B).
  • an anhydride may form next to another anhydride in its molecular chain or it may form next to a free carboxyl group, and the different chemical environments of the 5-membered anhydride intermediates of PMA causes band broadening in the infrared spectra.
  • the anhydride of PMA also absorbs at higher frequency than those of MA and I A, because the conjugation of the carbonyl and the alkene double bond of MA and I A lowers the anhydride carbonyl stretching bands frequencies (Bellamy, K.J. (1975), "The Infrared Spectra of Complex Molecules. 3 rd ed., Chapman and Hall, London, pp. 144-145; Clothup, N.B. et al. (1990), "Introduction to Infrared and Raman Spectroscopy," Ch. 9, Academic Press, San Diego, CA, pp. 310-312).
  • the cotton fabric was treated with 6.7 %> IA, 4.0%> NaH 2 PO 2 in combination with K 2 S 2 O 8 of different concentrations (0.00, 0.25, 0.50, 1.00 and 2.00 %>).
  • the fabric samples were then cured at 180 ° C for 2 min.
  • the difference spectra of the cotton fabric samples thus treated (the fabric after curing minus that before curing) are presented in Figure 1 1.
  • the anhydride carbonyl has its symmetric and asymmetric stretching modes at 1843 and 1768 cm 1 , respectively, in the difference spectrum (Figure 1 IA).
  • the performance of the treated cotton fabric was evaluated.
  • the WRA (wrinkle recovery angle) of the cotton fabric treated with 6.7%> IA and 4.0%) NaH 2 PO 2 in combination with K 2 S 2 O 8 of different concentrations is shown in Table 4.
  • the WRA of the cotton fabric increases from 200 to 241 degree when the fabric is treated without K 2 S 2 O 8 . It increases further to 262 degree when 0.25% K 2 S 2 O 8 is present in the finishing solution. WRA increases moderately as the K 2 S 2 O 8 concentration increases in the system.
  • the fabric treated with 6.7%) IA and 4.0%) NaH 2 PO 2 without K 2 S 2 O g shows WRA of 227 degree. When 0.25%) K 2 S 2 O 8 is presented in the finishing system, however, the WRA increases to 262 degree.
  • the WRA of the cotton fabric treated with 6.0%> MA and 4.0% NaPI 2 PO 2 in combination with K 2 S 2 O 8 of different concentrations is also included in Table 4.
  • the WRA of the treated fabric increases when K 2 S 2 O 8 is present in the finish solution.
  • K 2 S 2 O 8 concentration has a profound impact on the WRA of the MA-treated fabric after 10 washing cycles (Table 4).
  • the significant improvement in the fabric wrinkle- resistance in the presence of K 2 S 2 O 8 in the finish system and the effect of K 2 S 2 O 8 concentration on the wrinkle-resistance of the treated fabric are indicative of the in-situ polymerization of I A and MA on the fabric and ester crosslinking of the cotton fabric by the polymers, and are consistent with all the data presented above.
  • Table 5 Presented in Table 5 are the WRA, DP rating and mechanical strength of the cotton fabric treated with formations containing different acids and different K 2 S 2 O 8 concentrations.
  • DP rating is a standard rating system for fabric smoothness with 5 being the best and 1 being the worst with many wrinkles.
  • w, f and w + f take their standard meaning as known in the art with w being the warp direction in fabric, and f indicating filling direction.
  • w + f is the sum of w and f.
  • the performance of the fabric treated with 1,2,3,4- butanetetracarboxylic acid (BTCA) is also included for the purpose of comparison.
  • the mechanical strength of the three treated fabric samples is similar to or somewhat lower than that of the BTCA-treated fabric, probably because the acids concentration of the three formations is higher than that of BTCA, and therefore those three formulations causes more acid degradation of cellulose than that of BTCA.
  • the initiator concentration used is usually less than 1%> of monomer.
  • the K 2 S 2 O 8 concentration in the finish system was 1.5% of the weight of the monomers (Choi, H.-M. (1992), "Nonformaldehyde Polymerization- Crosslinking treatment of Cotton Fabrics for Improved Strength Retention,” Textile Res. J. 62:614-618).
  • the K 2 S 2 O 8 concentration was found to have a profound effect on the in-situ polymerization, and the K 2 S 2 O 8 concentration required to achieve the in-situ polymerization with significant quantity is much higher than the concentrations conventionally used for free-radical chain polymerization.

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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un système d'amorçage de polymérisation comprenant un générateur de radicaux libres et un agent réducteur phosphoré. Ce système convient, d'une part à la polymérisation de composés oléfiniquement insaturés contenant au moins deux groupes carboxyle, et d'autre part à la formation de polymères sur des substrats cellulosiques.
PCT/US2000/040990 1999-09-24 2000-09-25 Systeme d'amorçage a radicaux libres et procede de polymerisation d'acides ethyleniques dicarboxyliques WO2001021677A1 (fr)

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AU14922/01A AU1492201A (en) 1999-09-24 2000-09-25 Free radical initiation system and method of polymerizing ethylenical dicarboxylic acids

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US15610399P 1999-09-24 1999-09-24
US60/156,103 1999-09-24

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2003033812A1 (fr) * 2001-10-18 2003-04-24 The Procter & Gamble Company Composition d'appret pour textiles et procedes d'utilisation associes
US6841198B2 (en) 2001-10-18 2005-01-11 Strike Investments, Llc Durable press treatment of fabric
US6989035B2 (en) 2001-10-18 2006-01-24 The Procter & Gamble Company Textile finishing composition and methods for using same
US7008457B2 (en) 2001-10-18 2006-03-07 Mark Robert Sivik Textile finishing composition and methods for using same
US7018422B2 (en) 2001-10-18 2006-03-28 Robb Richard Gardner Shrink resistant and wrinkle free textiles
US7169742B2 (en) 2001-10-18 2007-01-30 The Procter & Gamble Company Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents
WO2014143773A1 (fr) 2013-03-15 2014-09-18 Lubrizol Advanced Materials, Inc. Polymères d'acide itaconique
WO2015138872A1 (fr) 2014-03-14 2015-09-17 Lubrizol Advanced Materials, Inc. Polymères et copolymères d'acide itaconique
CN114478885A (zh) * 2021-12-17 2022-05-13 科威天使环保科技集团股份有限公司 一种具有大分子结构的寡聚膦基琥珀酸及其制备方法

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US4709091A (en) * 1984-04-06 1987-11-24 Kao Corporation Production of polymaleic acid
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US5268437A (en) * 1992-01-22 1993-12-07 Rohm And Haas Company High temperature aqueous polymerization process
US5336744A (en) * 1993-03-17 1994-08-09 Rohm And Haas Company Process for polymerization of itaconic acid
US5574120A (en) * 1994-11-09 1996-11-12 Chemische Fabrik Stockhausen Gmbh Process for the preparation of dicarboxylic acid terpolymers for detergents and cleaning agents

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US3869432A (en) * 1970-04-28 1975-03-04 Champion Int Corp Styrene-maleic anhydride complex and process for making same
US4709091A (en) * 1984-04-06 1987-11-24 Kao Corporation Production of polymaleic acid
US5135677A (en) * 1988-04-11 1992-08-04 Nippon Shokubai Co., Ltd. Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer
US5268437A (en) * 1992-01-22 1993-12-07 Rohm And Haas Company High temperature aqueous polymerization process
US5336744A (en) * 1993-03-17 1994-08-09 Rohm And Haas Company Process for polymerization of itaconic acid
US5574120A (en) * 1994-11-09 1996-11-12 Chemische Fabrik Stockhausen Gmbh Process for the preparation of dicarboxylic acid terpolymers for detergents and cleaning agents

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033812A1 (fr) * 2001-10-18 2003-04-24 The Procter & Gamble Company Composition d'appret pour textiles et procedes d'utilisation associes
US6841198B2 (en) 2001-10-18 2005-01-11 Strike Investments, Llc Durable press treatment of fabric
US6989035B2 (en) 2001-10-18 2006-01-24 The Procter & Gamble Company Textile finishing composition and methods for using same
US7008457B2 (en) 2001-10-18 2006-03-07 Mark Robert Sivik Textile finishing composition and methods for using same
US7018422B2 (en) 2001-10-18 2006-03-28 Robb Richard Gardner Shrink resistant and wrinkle free textiles
US7144431B2 (en) 2001-10-18 2006-12-05 The Procter & Gamble Company Textile finishing composition and methods for using same
US7169742B2 (en) 2001-10-18 2007-01-30 The Procter & Gamble Company Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents
US7247172B2 (en) 2001-10-18 2007-07-24 The Procter & Gamble Company Shrink resistant and wrinkle free textiles
WO2014143773A1 (fr) 2013-03-15 2014-09-18 Lubrizol Advanced Materials, Inc. Polymères d'acide itaconique
WO2015138872A1 (fr) 2014-03-14 2015-09-17 Lubrizol Advanced Materials, Inc. Polymères et copolymères d'acide itaconique
CN114478885A (zh) * 2021-12-17 2022-05-13 科威天使环保科技集团股份有限公司 一种具有大分子结构的寡聚膦基琥珀酸及其制备方法

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