US3189578A - Polymers and their production - Google Patents

Polymers and their production Download PDF

Info

Publication number
US3189578A
US3189578A US80831059A US3189578A US 3189578 A US3189578 A US 3189578A US 80831059 A US80831059 A US 80831059A US 3189578 A US3189578 A US 3189578A
Authority
US
United States
Prior art keywords
reaction
water
polymers
yarns
diisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Other languages
English (en)
Inventor
Henry R Kuemmerer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deering Milliken Research Corp
Milliken Research Corp
Original Assignee
Milliken Research Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL250774D priority Critical patent/NL250774A/xx
Priority to NL261869D priority patent/NL261869A/xx
Priority to BE600844D priority patent/BE600844A/xx
Priority to NL127106D priority patent/NL127106C/xx
Application filed by Milliken Research Corp filed Critical Milliken Research Corp
Priority to US80831059 priority patent/US3189578A/en
Priority to US80829759 priority patent/US3061470A/en
Priority to US1227060 priority patent/US3061472A/en
Priority to US12269A priority patent/US3061471A/en
Priority to GB1383960A priority patent/GB928049A/en
Priority to FR824735A priority patent/FR1279244A/fr
Priority to CH456760A priority patent/CH370739A/fr
Priority to CH642361A priority patent/CH398974A/fr
Priority to DE19601419423 priority patent/DE1419423A1/de
Priority to DE19611419518 priority patent/DE1419518A1/de
Priority to CH240361A priority patent/CH416539A/de
Priority to CH296862A priority patent/CH407938A/de
Priority to FR854135A priority patent/FR1282904A/fr
Priority to GB744661A priority patent/GB931681A/en
Application granted granted Critical
Publication of US3189578A publication Critical patent/US3189578A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/84—Chemically modified polymers by aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives 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
    • D06M15/21—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
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/04—Polyester fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/18—Grafting textile fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3049—Including strand precoated with other than free metal or alloy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3179—Woven fabric is characterized by a particular or differential weave other than fabric in which the strand denier or warp/weft pick count is specified
    • Y10T442/322—Warp differs from weft
    • Y10T442/3228—Materials differ

Definitions

  • Another object of the invention is the provision of a synthetic size which may be easily desized with plain water and dumped into streams without seriously polluting them.
  • Another object of the invention is the provision of an inexpensive method of advantageously sizing and desizing textile yarns while substantially eliminating stream pollution problems.
  • novel polymers of this invention are particularly characterized by their water-solubility and their filmforming properties. They are readily water soluble, making them easy to apply to textile yarns as a size, and they retain their solubility so that desizing may be accomplished by a simple water wash.
  • Thefilms formed from water solutions of these new polymers are very tough and flexible and strong, especially as contrasted with the brittle films of the polyethylene ether glycol polymers alone and the prior art materials produced with water-insoluble reaction products of polyalkylene ether glycols and aryl diisocyanates, which materials are sometimes rubbery and sometimes crumbly.
  • spun Dacron yarns for example, are so adhesively bound by the size of this invention that their diameter is actually substantially reduced by the sizing operation while the same yarns separate at a greater distance ahead of the split rods than the same yarns sized with conventional materials.
  • one molar equivalent of a substantially anhydrous polymer of polyalkylene ether glycol having a molecular weight of from about 6,000 to 7,500 is catalytically reacted with from about 1 to 2 molar equivalents of an aryl diisocyanate (in practice slightly more than 1 mol is required and less than 2 mols is needed to avoid the danger of rapidly forming water-insoluble polymers) to produce polymers of extremely high molecular weight and the reaction is abruptly halted at a point just short of Water insolubility.
  • the molar ratio is from about 1%:1 to ll zzl of diisocyanate to glycol, respectively. The molar ratio is extremely important as too much diisocyanate rapidly produces water-insoluble products and too little diisocyanate produces brittle polymers which make weak films which are unsuitable for sizing purposes.
  • the abrupt halting of the reaction may be accomplished by the addition of an aliphatic monohydroxy alcohol as a stopping agent which reacts with isocyanate radicals to block further reaction with the glycol.
  • Aliphatic mono-- hydroxy alcohols are preferred, as polymers so stopped have been found to maintain better weaving efliciency over a period of time when used as a size.
  • Methanol and isopropanol being both inexpensive and efficient, are excellent stopping agents tor -abruptly halting the polymerization reaction at the right point.
  • the minimum amount of stopping agent to be added will vary according to the excess of diisocyanate used. While a theoretical minimum may be readily calculated, it is preferred to add at least a molar equivalent for the isocyanate used, as a safe excess. Additional quantities are ordinarily not harmful.
  • reaction should proceed as far as reasonably possible short of the point of water-insolubility to obtain polymers having the most desirable film strength.
  • products made in accordance with this invention may be made by duplicating the conditions except that reaction is halted at a time less than time X and greater than of X.
  • the polymerization time and temperature may be varied over a considerable range so long as the react-ion is stopped at the critical point.
  • the reaction must be carried out at a temperature above the melting point of the polyalkylene ether glycol. However, the reaction proceeds slowly unless the temperature -is elevated above about 70 C. but the temperature should not exceed 150 C. because higher temperatures tend to decompose the polyoxyalkylene chains.
  • the preferred range is from about 100 C. to 150 C.
  • the time of the reaction is a function of the temperature, the reactants, the catalyst and other factors. Suitable times have varied from 8 minutes to about an hour.
  • polyalkylene ether glycols refers to polyethers which are derived from alkylene oxides or glycols or from other heterocylic ethers such as dioxolane, and which may be represented by the formula HO(RO) H, in which R stands for a lower alkylene radical and n is an integer greater than 1. Not all the alkylene radicals present need be the same, and polyethers containing a mixture of radicals can be used, although the choice of radicals should be such that the resulting polymer is water soluble. These polyalkylene ether glycols are waxy solids.
  • the preferred glycols are polyethylene ether glycols.
  • aryl diisocyanates may be used in this invention, .but monophenyl diisocyanate: are preferred. Suitable compounds include 2,4-toluene diisocyanate, mphenylene diisocyanate, 4-chloro'1,3-phenylene diisocyanate, met-hyl'ene-bis-(t-phenyl isocyanate), naphthalene- 1,5-d-iisocyanate and the like.
  • Any catalyst known to be useful in the reaction of polyalkylene ether glycols with aryl diisocyanates may be used in the present invention including the tertiary organic bases of US. Patent No. 2,692,874 such as triethylamine, pyridine, tri-n-butylphosphine, their acid salts and the like.
  • organo-metal salts such as cobalt naphthenate and similar salts of lead, zinc, copper and manganese.
  • the organic radicals may be either aliphatic or aromatic residues.
  • substantially anhydrous polymer is used to define a polymer containing less than about 0.5% moisture. It has been found that some commercial polyalkylene ether glycols containing as much as 0.5% moisture react improperly to provide films of poor strength, making them unsuitable for textilesizes. In practice, the moisture content of the polyalkylene ether glycols will be kept as low as possible.
  • the amount of silicone used will be from about 0.01% to 1% and preferably about 0.25%. Somewhat larger quantities may be used in some instances but such uses are merely wasteful. Furthermore, it has been found that raising the addition of ammonia to raise the pH of the solution to about pH 8.5-9.5 also provides a definite improvement in weave room performance, apparently by reduction of any tendency of the polymers to pick-up moisture.
  • the amount of size to be applied will vary somewhat according to the nature of the fibrous materials, the type of yarn, the denier or count and the like but in general 2.5% to 5% polymer solids on the weight of the yarn provides a suitable size.
  • the concentration of the sizing solution may vary over a fairly wide range of from about 2% to 15% but a 4% to 8% solution of the p y is P eferred.
  • hygroscopic properties of the polymer In sizing operations, as distinguished from fruit and vegetable coating and the like, hygroscopic properties of the polymer must be minimized because Weaving is normally done under very high humidity conditions.
  • the use of polyurethanes end-blocked with alkoxy groups, i.e., alcohol stopped reaction products of the invention, has been found to be particularly valuable interms of lowered hygroscopic tendencies. Silicones are very eifective in reducing any stickiness which may tend to occur as a result of moisture pick-up of hygroscopic polymers.
  • the silicone rises through the polymers of aryl diisocyanate and polyalkylene ether glycol when mixtures of the two are cast into films from an aqueous medium.
  • This provides a sort of two layer effect permitting the hydrophobic properties of the silicone to 'be eifectively utilized.
  • aqueous medium containing an alcohol stopped watersoluble polymer of the invention and a silicone with the medium having a controlled pH of from about 8.5-9.5.
  • Yarns sized in accordance with this preferred procedure have a coating of polymer topped by a coating of silicone.
  • the stability of-the polymer in solution is excellent so that it may be stored in any-of its liquid or solid forms and its good water solubility permits mixing at any point in the mill whereby a separate mixing operation and operator, as required for starch sizing, may be eliminated.
  • yarn includes both spun fiber yarns and filament yarns.
  • the invention is particularly applicable to spun Dacron, spun mixtures" of cotton and Dacron, cotton, viscose and acetate and the like.
  • the polymers of this invention may be further reacted in situ on yarn to provide the desired products.
  • formaldehyde, acetaldehyde, acrolein, other aldehydes, and/or aldehyde donors such as methylol melamines, methylol ureas, methylol ethylene ureas, copolymers of acetone and formaldehydes, methylol acetylene diureas and the like may be added to the sizing solution preferably in the presence of an acidic catalyst so that they will react with the polymer on the slasher dry cans to produce water-insoluble cross-linked films on the yarn.
  • Example 1 92 pounds of substantially anhydrous polyethylene ether glycol in a molecular weight range of 6000-7500 (Carbowax 6000) was melted in a 50 gallon reactor equipped with a reflux condenser and a stirrer. When the temperature reached 70 C.,4 pounds and 3 ounces of 2,4-toluene diisocyanate (Nacconate was added: with stirring.
  • Example 2 The reaction proceeded as in Example 1, except that the smaller quantity required less time for reaction to the same point and reaction was topped with water rather than methanol. The appearance of the two solution products was not distinguishable to the naked eye.
  • the product of this example had a viscosity of 333 centipoises.
  • Example 3 A warp of several thousand ends of 100% spun Dacron yarns was sized on conventional synthetic slasher equipment having a heated size-box, standard squeeze rolls and Teflon-coated dry cans.
  • the yarns were impregnated by passing them through the size box containing a water solution of the product of Example 1 diluted to 6% solids and brought to pH 9 with ammonia.
  • the size box temperature was kept at 150 F. and the squeeze rolls were set to leave 3.5% solids on the yarn. Drying was completely conventional with dry can temperatures of about 200 F.
  • the slasher operated smoothly without hard size problem, with no sticking on the cans and excellent action was noted at the split rods. It appears as though splitting might be a smooth tear for no jagged edges were noted at the split lines and the split ran back from the rods a greater distance than normal.
  • a beam of the sized yarns was placed on a loom and readily woven into an all Dacron fabric of standard plainweave construction. Good weaving etficiency was noted immediately and shedding was minimized.
  • Example 4 In a suitable reaction vessel there is placed 50 parts by weight of dimethyl silicone oil (5000 centipoises), 20 parts by weight of perchlorethylene, 25 parts toluene, and 5 parts oleic acid. The resulting mixture agitated until solution was complete.
  • a size mixture was prepared as in Example 3 except there was dispersed in the aqueous mixture 2% by weight of the above silicone solution. The size mixture was then applied according to the procedure of Example 3 to a warp of several thousand ends of 100% spun polyethylene terephthalate (Dacron) yarns. The sized yarns appeared to have more lubricity than those from the preceding example, and this may account for the even greater weaving efficiency noted.
  • Example 5 To prepare a loom finished fabric, an all cotton warp was sized with a 5% solution of a product prepared in accordance with Example 3 to deposit 5% solids (weight basis) thereon. At the time of mixing the sizing solution (just prior to use), 0.1% of formaldehyde was added. A conventional cotton slasher was used with the size box heated to a temperature of F. Excellent running conditions were noted as in Example 4. The sized warp was woven into an all cotton fabric. Weaving efiiciency was good and shedding was minimized.
  • the size film had become insoluble and could not be washed out, thus providing a high-quality loom finished cotton fabric.
  • a water-soluble polyurethane which forms tough, flexible and strong films from water solutions thereof and which is a reaction product of an arylene diisocyanate and a polyethylene ether glycol of the formula HO(CH CH O) H wherein n is an integer sufficient to provide a molecular weight of from 6,000 to 7,500, said arylene diisocyanate being present in a molar ratio of 1%:1 to 1% :1 moles of arylene diisocyanate per mole of polyethylene ether glycol, said reaction having been terminated with at least one molar equivalent of an aliphatic monohydroxy alcohol per molar equivalent of said arylene diisocyanate when the reaction product had approached but not;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paper (AREA)
US80831059 1959-04-23 1959-04-23 Polymers and their production Expired - Lifetime US3189578A (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
NL250774D NL250774A (ru) 1959-04-23
NL261869D NL261869A (ru) 1959-04-23
BE600844D BE600844A (ru) 1959-04-23
NL127106D NL127106C (ru) 1959-04-23
US80831059 US3189578A (en) 1959-04-23 1959-04-23 Polymers and their production
US80829759 US3061470A (en) 1959-04-23 1959-04-23 Sizing textile yarns
US12269A US3061471A (en) 1959-04-23 1960-03-02 Sizing hydrophobic fibers with graft copolymers of gelatinized starch and acrylates
US1227060 US3061472A (en) 1959-04-23 1960-03-02 Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof
GB1383960A GB928049A (en) 1959-04-23 1960-04-20 Method of sizing textile yarns
FR824735A FR1279244A (fr) 1959-04-23 1960-04-20 Nouveaux polymères de polyoxyalkylène glycols et de diisocyanates et emploi de ces produits en particulier dans l'encollage des fils textiles
CH456760A CH370739A (fr) 1959-04-23 1960-04-22 Procédé d'encollage des fils textiles, fil textile obtenu par ce procédé et solution pour la mise en oeuvre de ce procédé
CH642361A CH398974A (fr) 1959-04-23 1960-04-22 Procédé de préparation de polymères
DE19601419423 DE1419423A1 (de) 1959-04-23 1960-04-23 Polymere sowie deren Herstellung und Verwendung
CH240361A CH416539A (de) 1959-04-23 1961-02-28 Verfahren zum Schlichten von hydrophoben Textilfasern
DE19611419518 DE1419518A1 (de) 1959-04-23 1961-02-28 Schlichten von hydrophoben Fasern
CH296862A CH407938A (de) 1959-04-23 1961-02-28 Schlichte für hydrophobe Textilfasern und Verfahren zur Herstellung derselben
FR854135A FR1282904A (fr) 1959-04-23 1961-02-28 Procédé d'encollage des fibres hydrophobes
GB744661A GB931681A (en) 1959-04-23 1961-03-01 Sizing of hydrophobic fibres

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US80829759 US3061470A (en) 1959-04-23 1959-04-23 Sizing textile yarns
US80831059 US3189578A (en) 1959-04-23 1959-04-23 Polymers and their production
US1227060 US3061472A (en) 1959-04-23 1960-03-02 Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof
DED0033182 1960-04-23

Publications (1)

Publication Number Publication Date
US3189578A true US3189578A (en) 1965-06-15

Family

ID=27436759

Family Applications (3)

Application Number Title Priority Date Filing Date
US80829759 Expired - Lifetime US3061470A (en) 1959-04-23 1959-04-23 Sizing textile yarns
US80831059 Expired - Lifetime US3189578A (en) 1959-04-23 1959-04-23 Polymers and their production
US1227060 Expired - Lifetime US3061472A (en) 1959-04-23 1960-03-02 Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US80829759 Expired - Lifetime US3061470A (en) 1959-04-23 1959-04-23 Sizing textile yarns

Family Applications After (1)

Application Number Title Priority Date Filing Date
US1227060 Expired - Lifetime US3061472A (en) 1959-04-23 1960-03-02 Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof

Country Status (6)

Country Link
US (3) US3061470A (ru)
BE (1) BE600844A (ru)
CH (4) CH398974A (ru)
DE (2) DE1419423A1 (ru)
GB (2) GB928049A (ru)
NL (3) NL261869A (ru)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3321819A (en) * 1964-12-24 1967-05-30 Union Carbide Corp Process for sizing and desizing textile fibers
US3350361A (en) * 1962-07-31 1967-10-31 Lankro Chem Ltd Urethane polymers and methods of applying compositions containing the polymers
US3384623A (en) * 1964-01-11 1968-05-21 Toyo Spinning Co Ltd Production of polyurethane elastomers
US3402149A (en) * 1964-12-04 1968-09-17 Thiokol Chemical Corp Process for preparing polyureapolyurethane molding powders
US3427272A (en) * 1968-03-22 1969-02-11 Deering Milliken Res Corp Water-soluble polyurethane produced by reacting an aldehyde and the reaction product of an organic diisocyanate and an anhydrous polyalkylene ether glycol
US3427192A (en) * 1964-05-20 1969-02-11 Deering Milliken Res Corp Textile sizing composition
US3472802A (en) * 1966-11-23 1969-10-14 Inter Chem Corp Novel nitrocellulose flexographic printing inks
US3864195A (en) * 1972-01-27 1975-02-04 Henry G Patterson Stable synthetic carpet backing material
USB497473I5 (ru) * 1973-08-16 1976-02-03
US3982986A (en) * 1973-05-29 1976-09-28 Inmont Corporation Laminates and method of making them
US4079028A (en) * 1975-10-03 1978-03-14 Rohm And Haas Company Polyurethane thickeners in latex compositions
US4082703A (en) * 1975-04-07 1978-04-04 Union Carbide Corporation Polyurethane prepolymers, rebonded polyurethane foam and methods of forming the same
US4150946A (en) * 1975-11-04 1979-04-24 Rhone-Poulenc Industries Water-soluble polyurethanes and compositions and application thereof to substrates
US4155892A (en) * 1975-10-03 1979-05-22 Rohm And Haas Company Polyurethane thickeners for aqueous compositions
US4524036A (en) * 1981-08-10 1985-06-18 University Of Liverpool Process for the manufacture of polyurethane resin for electrostatic spinning
US4530876A (en) * 1983-08-12 1985-07-23 Ppg Industries, Inc. Warp sizing composition, sized warp strands and process
US4762751A (en) * 1984-07-30 1988-08-09 Ppg Industries, Inc. Flexible, chemically treated bundles of fibers, woven and nonwoven fabrics and coated bundles and fabrics thereof
US4762750A (en) * 1986-05-22 1988-08-09 Ppg Industries, Inc. Flexible, chemically treated bundles of fibers and process
US4863994A (en) * 1988-06-24 1989-09-05 The Dow Chemical Company Use of monohydric alcohols in molded polyurethane resins
US20090286864A1 (en) * 2007-06-01 2009-11-19 Taewoong Medical Co., Ltd. Coating agent for drug releasing stent, preparation method thereof and drug releasing stent coated therewith

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE633065A (ru) * 1962-05-30 1900-01-01
US3271342A (en) * 1963-02-04 1966-09-06 Deering Milliken Res Corp Composition comprising a salt of a styrene-maleic acid copolymer and a polyurethane
US3301644A (en) * 1963-03-14 1967-01-31 Deering Milliken Res Corp Flexible resin-impregnated cloth buff
US3425973A (en) * 1963-08-09 1969-02-04 Du Pont Coating composition based on aromatic diisocyanates,polyols,and monohydric alcohols
DE1218990B (de) * 1963-10-19 1966-06-16 Bayer Ag Verfahren zur Praeparation von selbstverklebenden Elastomerfaeden
US3402148A (en) * 1964-07-06 1968-09-17 Thiokol Chemical Corp Easily processable, bloom-resistant, urethane gums and vulcanizates
US3377302A (en) * 1966-01-18 1968-04-09 Agriculture Usa Saponified starch acrylate grafts
US3497441A (en) * 1967-05-16 1970-02-24 Joseph Paksi Electrophoresis system and method
BE759114A (fr) * 1969-11-25 1971-05-18 Marles Kuhlmann Wyandotte Polymeres urethane-uree solubles dans l'eau
US3660010A (en) * 1969-12-17 1972-05-02 Nat Starch Chem Corp Treating textiles with soil release agents
US4061618A (en) * 1975-05-07 1977-12-06 National Starch And Chemical Corporation Process for preparing stable polyurethane latices
US4047533A (en) * 1976-09-20 1977-09-13 American Cyanamid Company Absorbable surgical sutures coated with polyoxyethylene-polyoxypropylene copolymer lubricant
US4043344A (en) * 1976-09-20 1977-08-23 American Cyanamid Company Non-absorbable surgical sutures coated with polyoxyethylene-polyoxypropylene copolymer lubricant
US4143014A (en) * 1977-11-09 1979-03-06 The Upjohn Company Novel compositions
DE2848431A1 (de) * 1978-11-08 1980-05-14 Bayer Ag Wasserloesliche, ultrafiltrierbare polyurethan-anionomere und ihre verwendung als schlichtemittel in der textilindustrie
US4228053A (en) * 1979-01-29 1980-10-14 The Upjohn Company Concrete preparation with aqueous solution of product from polyether with polymethylene polyphenyl polyisocyanate
USRE30474E (en) * 1979-03-13 1981-01-06 Burlington Industries, Inc. Hot melt size and yarn sized therewith and packages and fabrics of sized yarn
US4375535A (en) * 1980-04-28 1983-03-01 Standard Brands Incorporated Stable liquid, amylopectin starch graft copolymer compositions
US4301017A (en) * 1980-04-28 1981-11-17 Standard Brands Incorporated Stable, liquid starch graft copolymer composition
US4690996A (en) * 1985-08-28 1987-09-01 National Starch And Chemical Corporation Inverse emulsions
DE3627594A1 (de) * 1986-08-14 1988-02-18 Basf Ag Leimungsmittel fuer papier auf basis feinteiliger waessriger dispersionen
DE3702712A1 (de) * 1987-01-30 1988-08-11 Basf Ag Leimungsmittel fuer papier auf basis feinteiliger waessriger dispersionen
GB8715736D0 (en) * 1987-07-03 1987-08-12 Harlow Chem Co Ltd Adhesive compositions
US5416181A (en) * 1989-02-10 1995-05-16 Penford Products Company Reinforced films made from water soluble polymers
US5003022A (en) * 1989-02-10 1991-03-26 Penford Products Company Starch graft polymers
US5055541A (en) * 1989-06-27 1991-10-08 Sequa Chemicals, Inc. Starch polymer graft composition and method of preparation
US5116890A (en) * 1989-06-26 1992-05-26 Sequa Chemicals, Inc. Non-formaldehyde self-crosslinking latex
US5026746A (en) * 1989-06-26 1991-06-25 Sequa Chemicals, Inc. Starch based binder composition for non-woven fibers or fabrics
DE69033492T2 (de) * 1990-01-09 2000-12-14 Dai-Ichi Kogyo Seiyaku Co., Ltd. Verfahren zur Herstellung von porösen Formkörpern aus Kunstharz, von ultrafeinen Fasern und von Vliesstoffen mit ultrafeinen Fasern
DE4133193A1 (de) * 1991-10-07 1993-04-08 Basf Ag Waessrige polymerisatdispersionen
US6051107A (en) * 1997-04-28 2000-04-18 Hercules Incorporated Process for surface sizing paper and paper prepared thereby
GB9807426D0 (en) * 1998-04-08 1998-06-03 Ici Plc Environmentally friendly aqueous architectural coating compositions
US6114417A (en) * 1998-10-16 2000-09-05 Cytec Technology Corp. Paper sizing agents and methods
US20040065425A1 (en) * 2002-10-07 2004-04-08 Kemira Chemicals, Inc. Latex paper sizing composition
US9074079B2 (en) 2010-06-16 2015-07-07 Cargill, Incorporated Starch-based compositions for latex replacement
FR3024874B1 (fr) 2014-08-14 2016-09-02 Roquette Freres Copolymere de dextrine avec du styrene et un ester acrylique, son procede de fabrication et son utilisation pour le couchage papetier

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2284637A (en) * 1938-09-29 1942-06-02 Du Pont Polymeric carbamates and their preparation
US2871226A (en) * 1955-03-24 1959-01-27 Du Pont Elastomeric condensation products prepared from polyether glycols
US2871227A (en) * 1955-03-24 1959-01-27 Du Pont Elastomeric condensation products prepared from polyether glycols
US2946767A (en) * 1955-08-12 1960-07-26 Ciba Ltd Manufacture of reaction products of polyisocyanates with ethylene oxide addition products
US2948691A (en) * 1951-05-10 1960-08-09 Mobay Chemical Corp High molecular weight polyether urethane polymers
US2952665A (en) * 1955-12-08 1960-09-13 Mobay Chemical Corp High molecular weight cyclic trimers containing blocked isocyanate groups
US2977330A (en) * 1957-12-05 1961-03-28 Dow Chemical Co Cellular polyalkylene-etherglycolorganic diisocyanate reaction product and method of preparing same
US3021307A (en) * 1958-06-30 1962-02-13 Du Pont Polyurethane elastomers cured with paraformaldehyde

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA462398A (en) * 1950-01-10 Shawinigan Resins Corporation Polymerization process for vinylidene compounds
US2301509A (en) * 1939-10-21 1942-11-10 Rohm & Haas Fixation of sizes
US2385714A (en) * 1941-06-25 1945-09-25 Stein Hall & Co Inc Sizing and finishing compositions
US2662039A (en) * 1947-02-06 1953-12-08 Harris Res Lab Method of rendering organic textile material water repellent and composition therefor
GB703005A (en) * 1950-08-31 1954-01-27 Nat Starch Products Inc Emulsion copolymerization of vinyl monomers and mono-esters of unsaturated dicarboxylic acids
US2692874A (en) * 1951-07-19 1954-10-26 Du Pont Elastomers from polyalkylene ether glycol reacted with arylene diisocyanate and water
DE1073738B (de) * 1955-05-31 1960-01-21 E. I. du Pont de Nemours and Company, Wilmington Del. (V. St. A.) Verfahren zur Herstellung von elastomeren Kunststoffen aus reaktionsfähigen Polyurethanen und Düsocyanaten
US2914495A (en) * 1956-04-17 1959-11-24 Borden Co Water paint comprising pigment and aqueous emulsion of polyvinyl acetate and waxy maize starch
US2884394A (en) * 1956-08-20 1959-04-28 Hercules Powder Co Ltd Aqueous solutions of polyester resins prepared by reaction of a polyhydric alcohol, a partial allyl ether of pentaerythritol, and an unsaturated dicarboxylic acid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2284637A (en) * 1938-09-29 1942-06-02 Du Pont Polymeric carbamates and their preparation
US2948691A (en) * 1951-05-10 1960-08-09 Mobay Chemical Corp High molecular weight polyether urethane polymers
US2871226A (en) * 1955-03-24 1959-01-27 Du Pont Elastomeric condensation products prepared from polyether glycols
US2871227A (en) * 1955-03-24 1959-01-27 Du Pont Elastomeric condensation products prepared from polyether glycols
US2946767A (en) * 1955-08-12 1960-07-26 Ciba Ltd Manufacture of reaction products of polyisocyanates with ethylene oxide addition products
US2952665A (en) * 1955-12-08 1960-09-13 Mobay Chemical Corp High molecular weight cyclic trimers containing blocked isocyanate groups
US2977330A (en) * 1957-12-05 1961-03-28 Dow Chemical Co Cellular polyalkylene-etherglycolorganic diisocyanate reaction product and method of preparing same
US3021307A (en) * 1958-06-30 1962-02-13 Du Pont Polyurethane elastomers cured with paraformaldehyde

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350361A (en) * 1962-07-31 1967-10-31 Lankro Chem Ltd Urethane polymers and methods of applying compositions containing the polymers
US3384623A (en) * 1964-01-11 1968-05-21 Toyo Spinning Co Ltd Production of polyurethane elastomers
US3427192A (en) * 1964-05-20 1969-02-11 Deering Milliken Res Corp Textile sizing composition
US3402149A (en) * 1964-12-04 1968-09-17 Thiokol Chemical Corp Process for preparing polyureapolyurethane molding powders
US3321819A (en) * 1964-12-24 1967-05-30 Union Carbide Corp Process for sizing and desizing textile fibers
US3472802A (en) * 1966-11-23 1969-10-14 Inter Chem Corp Novel nitrocellulose flexographic printing inks
US3427272A (en) * 1968-03-22 1969-02-11 Deering Milliken Res Corp Water-soluble polyurethane produced by reacting an aldehyde and the reaction product of an organic diisocyanate and an anhydrous polyalkylene ether glycol
US3864195A (en) * 1972-01-27 1975-02-04 Henry G Patterson Stable synthetic carpet backing material
US3982986A (en) * 1973-05-29 1976-09-28 Inmont Corporation Laminates and method of making them
US3990839A (en) * 1973-08-16 1976-11-09 Hoechst Aktiengesellschaft Process for obtaining irregular shadow dyeings on polyester fibers and mixtures thereof
USB497473I5 (ru) * 1973-08-16 1976-02-03
US4082703A (en) * 1975-04-07 1978-04-04 Union Carbide Corporation Polyurethane prepolymers, rebonded polyurethane foam and methods of forming the same
US4079028A (en) * 1975-10-03 1978-03-14 Rohm And Haas Company Polyurethane thickeners in latex compositions
US4155892A (en) * 1975-10-03 1979-05-22 Rohm And Haas Company Polyurethane thickeners for aqueous compositions
US4150946A (en) * 1975-11-04 1979-04-24 Rhone-Poulenc Industries Water-soluble polyurethanes and compositions and application thereof to substrates
US4524036A (en) * 1981-08-10 1985-06-18 University Of Liverpool Process for the manufacture of polyurethane resin for electrostatic spinning
US4530876A (en) * 1983-08-12 1985-07-23 Ppg Industries, Inc. Warp sizing composition, sized warp strands and process
US4762751A (en) * 1984-07-30 1988-08-09 Ppg Industries, Inc. Flexible, chemically treated bundles of fibers, woven and nonwoven fabrics and coated bundles and fabrics thereof
US4762750A (en) * 1986-05-22 1988-08-09 Ppg Industries, Inc. Flexible, chemically treated bundles of fibers and process
US4863994A (en) * 1988-06-24 1989-09-05 The Dow Chemical Company Use of monohydric alcohols in molded polyurethane resins
US20090286864A1 (en) * 2007-06-01 2009-11-19 Taewoong Medical Co., Ltd. Coating agent for drug releasing stent, preparation method thereof and drug releasing stent coated therewith
US7994213B2 (en) * 2007-06-01 2011-08-09 Taewoong Medical Co., Ltd. Coating agent for drug releasing stent, preparation method thereof and drug releasing stent coated therewith

Also Published As

Publication number Publication date
CH240361A4 (ru) 1966-03-31
CH456760A4 (ru) 1963-03-29
GB928049A (en) 1963-06-06
NL261869A (ru) 1900-01-01
GB931681A (en) 1963-07-17
US3061472A (en) 1962-10-30
NL250774A (ru) 1900-01-01
CH407938A (de) 1966-02-28
DE1419423A1 (de) 1969-02-06
US3061470A (en) 1962-10-30
CH416539A (de) 1967-01-31
CH398974A (fr) 1966-03-15
CH370739A (fr) 1963-09-13
BE600844A (ru) 1900-01-01
NL127106C (ru) 1900-01-01
DE1419518A1 (de) 1968-10-03

Similar Documents

Publication Publication Date Title
US3189578A (en) Polymers and their production
US4111816A (en) Phosphorus-containing polyester and size compositions
US4048001A (en) Polyurethane textile adhesive
US3814578A (en) Treatment of textiles with glycidol-modified polyurethanes
US2567238A (en) Dicyandiamide and formaldehyde product and method of making
JPS5856580B2 (ja) 熱反応性ポリウレタンエマルジヨンの製造方法
US3044898A (en) Textile sizing composition, applicating method and resulting product
US4038296A (en) Alkylene oxide derivatives based on polytetrahydrofuran copolymers
US3687605A (en) Stabilization of wool through treatment with a reducing agent and a polymer or polymer forming materials
US3213049A (en) Method of forming an aqueous dispersion of polyurethane
US4053440A (en) Latex compositions sensitive to heat
US3086887A (en) Textile sizing
US3427192A (en) Textile sizing composition
US2915418A (en) Non-woven fibrous products
EP0697029B1 (de) Wässrige polymerdispersionen und ihre verwendung zur herstellung wasserdampfdurchlässiger beschichtungen
US2968581A (en) Method of insolubilizing polymeric hydroxyl-bearing compounds
US3529990A (en) Process of finishing textile materials
US3542505A (en) Treatment of textiles with aziridine-modified polyurethanes
US3870556A (en) Textile finishing compounds
US2892736A (en) Sizing polyester yarns with an ethylene-maleic interpolymer
US3981913A (en) Mono-substituted ureas
US3267079A (en) Water soluble alkylene oxide modified polyurethane composition
CN1315903C (zh) 给纤维质基材提供斥水性的含水组合物
US3738981A (en) Textile treating compositions,process of treating textiles and textile articles
US3828005A (en) Treatment of textiles with glycidolmodified polyurethanes