US3189578A - Polymers and their production - Google Patents
Polymers and their production Download PDFInfo
- 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
Links
- 229920000642 polymer Polymers 0.000 title description 28
- 238000004519 manufacturing process Methods 0.000 title description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- -1 POLYETHYLENE Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 18
- 238000004513 sizing Methods 0.000 description 15
- 229920001281 polyalkylene Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 229920004934 Dacron® Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000009941 weaving Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009990 desizing Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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;
Description
United States Patent 3,189,578 POLYMERS AND THEIR PRODUCTION Henry R. Kuemmerer, Walhalla, S.C., assignor to Deering Milliken Research Corporation, near Pendleton, S.C., a corporation of Delaware No Drawing. Filed Apr. 23, 1959, Ser. No. 808,310 6 Claims. (Cl. 260-775) the basic ingredient of textile yarn sizing formulas. Some advances have been made in the use of synthetic size materials other than modified starch, especially in connection with synthetic yarns. However, these advances have been painfully slow despite the urgent need to conquer the stream pollution problem created by starch being dumped into streams from desizing units. Earlier synthetic sizing materials have met with very limited success because of their high cost and because they are only use ful with a limited number of fibers. Dacron has been a particularly diflicult fiber to size with any prior art materials and spun Dacron yarn sizing has remained a major textile problem prior to this invention.
It is an object of this invention to provide a composition and process by which textile yarns in general and spun Dacron yarn in particular maybe readily sized on conventional equipment to provide excellent weaving ethciency and minimum shedding. 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.
It is one object of this invention to make high molecular weight, water-soluble, tough, flexible, film-forming polymers of polyalkylene ether glycols and aryl diisocyanates. Another object of the invention is the provision of control steps in the polymerization of polyalkylene ether glycols with aryl diisocyanates to control the properties of the polymers thus formed.
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. These and other objects of the invention will be more readily apparent from the following detailed description.
The 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.
These water-soluble reaction products of polyalkylene ether glycols and aryl diisocyanates have outstanding advantages over prior art sizing materials in weaving efiiciency and in terms of running efliciency on conventional Patented June 15, 1965 slashers. Good yarn penetration even in the absence of a separate wetting agent is obtained at temperatures of about 120-180 F. Hard size at the squeeze roll is substantially eliminated. There is no sticking on conventional drying cans. Separation of the yarns at the split rods is smooth and even, and broken ends seldom, if ever, appear. At the same time, the size holds the fibers of individual yarns in a very close, tight, unitary relationship for efiicient weaving. These last two seemly contradictory advantages are amply evidenced by the fact that 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.
POLYMER PREPARATION In making the polymers according to this invention 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. Preferably 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.
The reaction should proceed as far as reasonably possible short of the point of water-insolubility to obtain polymers having the most desirable film strength. For example, if the reaction is carried out under standardized conditions and water insolubil-ity is first found to occur after a certain time X, 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.
Many methods may be used to determine the end point at which the reaction should be stopped to obtain a polymer that will provide tough flexible films which are readily water-soluble. In commercial production where everything is standardized, an empirical time-temperature relationship may be established by trial and error. After a little experience with given materials, a skilled chemist can tell the end point by visual inspect-ion of the reaction massi.e. its viscosity, reaction to stirring, stringiness, etc. Also with any given reactants, empirical viscosity determinations may be used.
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.
The term polyalkylene ether glycols as used throughout the specification and claims 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.
A wide variety of 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.
However, it has been found that particularly good results are obtained by using 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.
The term 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.
SIZING PROCEDURE weaving efiiciency. 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.
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.
Surprisingly, 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.
Thus, in the preferred manner of sizing, one will use an 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.
The invention is described both in the specification. and
claims in terms of sizing textile yarns and it will be understood that the term 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.
In some instances a permanent size is desirable to provide a loom finished fabric. In such instances, the polymers of this invention may be further reacted in situ on yarn to provide the desired products. In these reactions, 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.
The invention will be better understood by reference to the following typical examples:
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.
183 grams of a 6% solution of cobalt naphthenate' was added forthwith to catalyze the reaction. At the end of the addition, the temperature had risen to 88 C. as heating was continued throughout the reaction. In about 20 minutes the reaction temperature reached C. This temperature was maintained for 15 minutes while stirring continued. At the end of the 15 minute period, 9 pounds of isopropanol were added and stirred into the mixture to halt the reaction and heating was stopped. Water was then added in a quantity suflicient to make a 25% solution of the polymer which was then ready for further dilution and use as a size.
After addition of the diisocyanate and catalyst, the reacting mass became more viscous as the reaction proceeded. Towards the end of the reaction period, the reaction mass was stiffening and would string out several inches behind a stirring rod. There was little change in physical appearance on addition of the methnnolexccpt Example 2 To 35 grams of molten (120 C.) polyethylene ether glycol of a molecular weight range of 6000-7500, there was added 1 gram of 2,4-toluene diisocyanate and 5 drops of cobalt naphthenate solution (6%). The temperature was maintained for 5 minutes after which water was added in a quantity suflicient to make a solution. 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.
Repeating this example using m-phenylene diisocyanate or methylene-bis-(4-phenyl isocyanate) (in 50% benzene solution) instead of 2,4-toluene diisocyanate produced products of similar appearance and utility as a size.
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.
Complete desizing was eflected by washing the woven fabric for 30 minutes in lukewarm water, even without a surface active agent.
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.
This example was repeated using methyl hydrogen silicone, chain stopped with trimethyl silicone, in the place of the dimethyl silicone oil and the results were substantially duplicated. Other silicones useful in the treatment of textiles may be substituted for those listed above or the coated yarns may be top coated with chlorosilane vapors if desired.
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.
Because of the formaldehyde, the size film had become insoluble and could not be washed out, thus providing a high-quality loom finished cotton fabric.
Those skilled in the art will find that certain changes may be made in the precise conditions, proportions and procedures set forth above without departing from the invention as defined in the claims.
Iclaim:
1. 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;
References Cited by the Examiner UNITED STATES PATENTS 2,284,637 6/42 Catlin 26077.5v 2,871,226 1/59 McShane 26077.5 2,871,227 1/59 Walter 26077.5 2,946,767 7/60 Gassmann 260- 77.5 2,948,691 8/60 Windemuth et al. 26077.5 2,952,665 9/60 Bunge 260453 2,977,330 3/61 Brower 26025 3,021,307 2/62 Csendes 26077.5
FOREIGN PATENTS 208,983 7/57 Australia.
LEON J. BERCOVITZ, Primary Examiner.
H. N. BURSTEIN, M. STERMAN, I. R. LIBERMAN,
Examiners.
Claims (1)
1. 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
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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 |
US12269A US3061471A (en) | 1959-04-23 | 1960-03-02 | Sizing hydrophobic fibers with graft copolymers of gelatinized starch and acrylates |
GB1383960A GB928049A (en) | 1959-04-23 | 1960-04-20 | Method of sizing textile yarns |
FR824735A FR1279244A (en) | 1959-04-23 | 1960-04-20 | New polymers of polyoxyalkylene glycols and diisocyanates and use of these products in particular in the sizing of textile yarns |
CH642361A CH398974A (en) | 1959-04-23 | 1960-04-22 | Polymer preparation process |
CH456760A CH370739A (en) | 1959-04-23 | 1960-04-22 | Process for sizing textile yarns, textile yarn obtained by this process and solution for implementing this process |
DE19601419423 DE1419423A1 (en) | 1959-04-23 | 1960-04-23 | Polymers and their manufacture and use |
DE19611419518 DE1419518A1 (en) | 1959-04-23 | 1961-02-28 | Sizing of hydrophobic fibers |
FR854135A FR1282904A (en) | 1959-04-23 | 1961-02-28 | Sizing process for hydrophobic fibers |
CH296862A CH407938A (en) | 1959-04-23 | 1961-02-28 | Sizing for hydrophobic textile fibers and process for producing the same |
CH240361A CH416539A (en) | 1959-04-23 | 1961-02-28 | Process for sizing hydrophobic textile fibers |
GB744661A GB931681A (en) | 1959-04-23 | 1961-03-01 | Sizing of hydrophobic fibres |
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US1227060 US3061472A (en) | 1959-04-23 | 1960-03-02 | Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof |
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US1227060 Expired - Lifetime US3061472A (en) | 1959-04-23 | 1960-03-02 | Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof |
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US1227060 Expired - Lifetime US3061472A (en) | 1959-04-23 | 1960-03-02 | Sizing hydrophobic fibers with acrylate polymers and gelatinized starch or graft copolymers thereof |
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Cited By (20)
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 |
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DE1218990B (en) * | 1963-10-19 | 1966-06-16 | Bayer Ag | Process for the preparation of self-adhesive elastomer threads |
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 (en) * | 1969-11-25 | 1971-05-18 | Marles Kuhlmann Wyandotte | WATER-SOLUBLE URETHANE-UREE POLYMERS |
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 |
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DE2848431A1 (en) * | 1978-11-08 | 1980-05-14 | Bayer Ag | WATER-SOLUBLE, ULTRA-FILTRATABLE POLYURETHANE ANIONOMERS AND THEIR USE AS A FINISHING AGENT IN THE TEXTILE INDUSTRY |
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 (en) * | 1986-08-14 | 1988-02-18 | Basf Ag | SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS |
DE3702712A1 (en) | 1987-01-30 | 1988-08-11 | Basf Ag | SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS |
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US5003022A (en) * | 1989-02-10 | 1991-03-26 | Penford Products Company | Starch graft polymers |
US5416181A (en) * | 1989-02-10 | 1995-05-16 | Penford Products Company | Reinforced films made from water soluble polymers |
US5026746A (en) * | 1989-06-26 | 1991-06-25 | Sequa Chemicals, Inc. | Starch based binder composition for non-woven fibers or fabrics |
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 |
EP0436966B1 (en) * | 1990-01-09 | 2000-03-22 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Methods for manufacture of porous resin mouldings, ultrafine fibres and ultrafine fibre nonwoven fabrics |
DE4133193A1 (en) * | 1991-10-07 | 1993-04-08 | Basf Ag | WAFER POLYMERISATE DISPERSIONS |
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 |
CA2802757A1 (en) | 2010-06-16 | 2012-01-05 | Stephane Biltresse | Starch-based compositions for latex replacement |
FR3024874B1 (en) | 2014-08-14 | 2016-09-02 | Roquette Freres | DEXTRIN COPOLYMER WITH STYRENE AND ACRYLIC ESTER, PROCESS FOR PRODUCING THE SAME AND USE THEREOF FOR PAPER COATING |
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0
- NL NL261869D patent/NL261869A/xx unknown
- BE BE600844D patent/BE600844A/xx unknown
- NL NL250774D patent/NL250774A/xx unknown
- NL NL127106D patent/NL127106C/xx active
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- 1959-04-23 US US80829759 patent/US3061470A/en not_active Expired - Lifetime
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- 1960-04-20 GB GB1383960A patent/GB928049A/en not_active Expired
- 1960-04-22 CH CH456760A patent/CH370739A/en unknown
- 1960-04-22 CH CH642361A patent/CH398974A/en unknown
- 1960-04-23 DE DE19601419423 patent/DE1419423A1/en active Pending
-
1961
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- 1961-02-28 DE DE19611419518 patent/DE1419518A1/en active Pending
- 1961-02-28 CH CH240361A patent/CH416539A/en unknown
- 1961-03-01 GB GB744661A patent/GB931681A/en not_active Expired
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Cited By (22)
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 (en) * | 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 |
---|---|
CH370739A (en) | 1963-09-13 |
CH456760A4 (en) | 1963-03-29 |
NL127106C (en) | 1900-01-01 |
NL250774A (en) | 1900-01-01 |
DE1419423A1 (en) | 1969-02-06 |
US3061472A (en) | 1962-10-30 |
BE600844A (en) | 1900-01-01 |
CH416539A (en) | 1967-01-31 |
CH407938A (en) | 1966-02-28 |
CH240361A4 (en) | 1966-03-31 |
NL261869A (en) | 1900-01-01 |
DE1419518A1 (en) | 1968-10-03 |
GB931681A (en) | 1963-07-17 |
US3061470A (en) | 1962-10-30 |
CH398974A (en) | 1966-03-15 |
GB928049A (en) | 1963-06-06 |
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