US3655821A - Polyamide filaments containing antistatic polyether prepared from a polyalkylene and an aliphatic dicarboxylic acid - Google Patents
Polyamide filaments containing antistatic polyether prepared from a polyalkylene and an aliphatic dicarboxylic acid Download PDFInfo
- Publication number
- US3655821A US3655821A US855469A US3655821DA US3655821A US 3655821 A US3655821 A US 3655821A US 855469 A US855469 A US 855469A US 3655821D A US3655821D A US 3655821DA US 3655821 A US3655821 A US 3655821A
- Authority
- US
- United States
- Prior art keywords
- acid
- polyglycol
- weight
- dicarboxylic acid
- filament
- 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
- 239000004952 Polyamide Substances 0.000 title description 13
- 229920002647 polyamide Polymers 0.000 title description 13
- 125000001931 aliphatic group Chemical group 0.000 title description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title description 4
- 239000004721 Polyphenylene oxide Substances 0.000 title description 2
- 229920001281 polyalkylene Polymers 0.000 title description 2
- 229920000570 polyether Polymers 0.000 title description 2
- 229920000151 polyglycol Polymers 0.000 abstract description 20
- 239000010695 polyglycol Substances 0.000 abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 18
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 18
- 229920001059 synthetic polymer Polymers 0.000 abstract description 16
- 239000007795 chemical reaction product Substances 0.000 abstract description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical group [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 1
- 239000002216 antistatic agent Substances 0.000 description 23
- 239000004744 fabric Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 229920005682 EO-PO block copolymer Polymers 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000012442 inert solvent Substances 0.000 description 5
- -1 naphthalene 2 Chemical compound 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000005108 dry cleaning Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000005521 carbonamide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- NLXFWUZKOOWWFD-UHFFFAOYSA-N 1-(2-hydroxyethylamino)-4-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCO)=CC=C2NC NLXFWUZKOOWWFD-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OOGKXQSCDZDEFV-UHFFFAOYSA-N 2-[(2-carboxyphenyl)diazenyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1N=NC1=CC=CC=C1C(O)=O OOGKXQSCDZDEFV-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- MCCYTOKKEWJAMY-UHFFFAOYSA-N 4-amino-n-(4-methoxy-1,2,5-thiadiazol-3-yl)benzenesulfonamide;5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidine-2,4-diamine Chemical compound COC1=NSN=C1NS(=O)(=O)C1=CC=C(N)C=C1.COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 MCCYTOKKEWJAMY-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- 241000543381 Cliftonia monophylla Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- YHUVMHKAHWKQBI-UHFFFAOYSA-N quinoline-2,3-dicarboxylic acid Chemical compound C1=CC=C2N=C(C(O)=O)C(C(=O)O)=CC2=C1 YHUVMHKAHWKQBI-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/15—Antistatic agents not otherwise provided for
- Y10S260/17—High polymeric, resinous, antistatic agents
-
- 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
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/91—Antistatic compositions
-
- 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
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/927—Polyamide admixed with oxyalkylene-containing polymer
Definitions
- a filament having antistatic properties, comprised of a hydrophobic synthetic polymer having mixed therethrough about 1 to 10 weight percent, based on the weight of the hydrophobic synthetic polymer, of the reaction product of a polyglycol which can be polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 100 to 15,000 and a compound which has the general formula:
- X is hydroxyl, -OR wherein. R is lower alkyl, or halogen and n is an integer from 2 to about 20.
- This invention relates to compositions suitable for use in imparting antistatic properties to textile materials, to methods for preparing such compositions, to methods employing such compositions for decreasing the tendency of textiles to collect static charges and to textiles so produced.
- Some antistatic agents have been found resistant to Washing or dry cleaning but they impart a harsh hand to yarns and fabrics or adversely affect the dyeability of the yarns and fabrics.
- the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof is an effective antistatic agent which can be mixed with a hydrophobic synthetic polymer prior to the extrusion of the synthetic polymer into a filament.
- the mixture of the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof throughout the hydrophobic synthetic filament produces yarns and fabrics containing the filaments which have excellent antistatic properties.
- the antistatic agents of the present invention resist Washing and dry cleaning since they are mixed throughout the filaments and do not impart a harsh hand to the yarns and fabrics.
- the antistatic agents of the present invention do not significantly affect the dyeability of the yarns and fabrics.
- a filament having antistatic properties comprised of a hydrophobic synthetic polymer having mixed therethrough about 1 to 10, preferably about 2 to 5, percent, based on the weight of the hydrophobic synthetic polymer, of the reaction product of a polyglycol which can be polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about to 15,000, preferably about 200' to 10,000, and a compound which has the general formula:
- the filament-forming hydrophobic synthetic polymer can be a polyolefin, polysulfone, polyphenyl oxide, polycarbonate, polyacrylonitrile, polyamide, polyester and the like or polymer blends thereof.
- suitable polymer blends as disclosed above are dispersions of polyester in polyamide such as disclosed in US. Pat. 3,369,057 to Twilley; US. Pats. 3,378,055, 3,378,056, and 3,378,602; British Pat. 1,097,068; Belgian Pat. 702,813; and Netherlands Pats. 6606838 and 6612628.
- the filament of the present invention can be prepared from these dispersions by known melt spinning techniques.
- the filament-forming synthetic polymer is a polyamide or a polyester.
- the filament of the present invention can be prepared from these polymers by known melt spinning techniques.
- Suitable polyamides for use in the present invention include, for example, those prepared by condensation of hexamethylene diamine and adipic acid, condensation of hexamethylene diamine and sebacic acid known as nylon 6,6 and nylon 6,10, respectively, condensation of his (para-aminocyclohexyl)methane and azelaic acid, condensation of bis(paraaminocyclohexyl)methane and dodecanedioic acid, or by polymerization of 6-caprolactam, 7-aminoheptanoic acid, 8-caprylactam, 9-arninopelargonic acid, ll-aminoundecanoic acid, and 12-dodecalactam, known as nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, and nylon 12, respectively.
- polyesters useful in the practice of this invention can be prepared in general by condensation reactions between dicarboxylic acids or their derivatives and compounds containing two hydroxyl groups, or materials possessing both an alcohol group and a carboxylic acid group or derivative thereof; or by polymerization of lactones.
- Dicarboxylic acid derivatives which can be employed include esters, salts, anhydrides and acid halides.
- the monomeric species employed in the preparation of the polyesters are preferably not more highly functional than difunctional in their reactivity so as to produce essentially linear, non-crosslinked polymer structures.
- Suitable polyesters for use in the present invention include those polymers in which one of the recurring units in the polyester chain is the diacylaromatic radical from terephthalic acid, isophthalic acid, S-t-butylisophthalic acid, a naphthalene dicarboxylic acid such as naphthalene 2,6 and 2,7 dicarboxylic acids, a diphenyl dicarboxylic acid, a diphenyl ether dicarboxylic acid, a diphenyl alkylene dicarboxylic acid, a diphenyl sulphone dicarboxylic acid, an azo dibenzoic acid, a pyridine dicarboxylic acid, a quinoline dicarboxylic acid, and analogous aromatic species including the sulfonic acid analogues, diacyl radicals containing cyclopentane or cyclohexane rings between the acyl groups; and such radicals substituted in the ring, e.g., by
- the dioxy radical representing the other principal recurring unit in the polyester chain can be an open chain aliphatic such as ethylene glycol or ether thereof, for example, the diether, or can contain rings such as those which form part of the above noted diacyl radicals.
- the carboxy and/or the oxy chain members can be directly attached to a ring or removed by one or more carbons therefrom, as in the 1,4 dioxymethyl cyclohexane radical.
- the preferred polyester is poly( ethylene terephthalate)
- Other suitable polyesters include poly(dimethylene cyclohexylene terephthalate) and poly(4-ethoxy benzoate).
- the antistatic agent of the present invention is the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof.
- Suitable polyglycols include polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide.
- the polyglycol can have a molecular weight from about 100 to 15,000, preferably about 200 to 10,000.
- Suitable compounds having the formula X-iJ-(OHM-i'J-X wherein X and n are defined above include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, pimelic acid and their corresponding acid halides such as chlorides and bromides and their lower alkyl esters.
- the (CH divalent radical in the above formula can be substituted with nonreactive groups such as p-phenylene, m-phenylene, and p-xylylene.
- the antistatic agents of the present invention can be prepared by any of the known methods.
- a typical method comprises charging into a flask, equipped with a heater, stirrer, reflux condenser and a thermometer, a polyethylene glycol having a molecular weight from about 100 to 15,000, preferably about 200 to 10,000; a compound which has the general formula:
- X is hydroxyl, --OR wherein R is lower alkyl, or halogen such as chlorine or bromine and n is an integer from 2 to about 20, preferably 2 to about and an inert solvent, such as dry xylene.
- the reaction mixture can then be heated to the boiling temperature of the reaction mixture and be reacted while refluxing in the presence of a catalytic amount of a suitable esterification catalyst such as p-toluene sulfonic acid or sulfuric acid.
- a suitable esterification catalyst such as p-toluene sulfonic acid or sulfuric acid.
- the above reaction is usually carried out for a period of about 2 to 8 hours.
- the reflux condenser can be replaced by a moisture trap and refluxing of the reaction mixture can be continued until no additional water appears in the moisture trap.
- the reaction mixture can then be cooled below its boiling temperature and the reaction flask can be set up to distill off the inert solvent.
- the distillation temperature should not be allowed to exceed about 150 to 175 C. and the inert solvent should not be distilled at a rate greater than about 2 to 4 ml. per minute.
- the reaction mixture can then be transferred to a thin film evaporator and the reaction mixture heated to a temperature of about 150 to 175 C. under a vacuum of about 1 to 10 mm. of mercury for a 4 period of time of about 2 to 6 hours or until no more volatiles can be removed.
- reaction mixture can be reacted in the thin film evaporator in the presence of little or no inert solvent as shown in Examples 2 and 3.
- the antistatic agents In general, it has been found desirable to prepare the antistatic agents by heating together one molecular portion of the polyglycol with from about 1.0 to 1.1 molecular portions of the dibasic acid. It is preferred that enough excess dibasic acid be added so that both ends of the antistatic agent have carboxyl end groups.
- the antistatic agent based upon the weight of the synthetic polymer, will produce the desired antistatic properties in the filament, however, it is preferred that about 2 to 5 weight percent be used.
- the antistatic agent can be mixed with the synthetic polymer during the polymerization, preferably at the end of the polymerization, of the synthetic polymer or can be mixed into the molten synthetic polymer by, for example, injection into the mixing portion of the extruder prior to the melt extrusion of the filament.
- the antistatic agent can be blended with the synthetic polymer granules prior to the melting of the synthetic polymer by conventional addition and mixing procedures.
- Example 1 Antistatic agents of the present invention were prepared in the following manner. Polyethylene glycol and an aliphatic dibasic acid were added to a one liter flask containing 500 ml. of dry xylene. The quantities of polyethylene glycol and aliphatic dibasic acid for each preparation are contained in Table I below. The one liter flask was equipped with a heater, stirrer, reflux condenser and a thermometer. The reaction mixture was heated to the boiling temperature of the reaction mixture and reacted while refluxing was in the presence of 0.1 gram p-toluene sulfonic acid catalyst at the boiling temperature of the reaction mixture for one hour.
- the reflux condenser was replaced by a Dean-Stark trap and refluxing of the reaction mixture was continued until no additional water appeared in the Dean- Stark trap.
- the reaction mixture was then cooled below its boiling temperature and the reaction flask was set up to distill oil? the xylene. The distillation temperature was not allowed to exceed C. and the xylene was distilled at a rate no greater than 10 ml. per minute. When most of the xylene was removed, the reaction mixture was then transferred to a 500 ml. Rinco thin film evaporator and the reaction mixture was heated to a temperature of about 150 to C. under a vacuum of about 2 mm. Hg until no more volatiles could be removed.
- Antistatic agents of the present invention were prepared in the following manner. Polyethylene glycol and an aliphatic dibasic acid were added to a 500 ml. Rinco thin film evaporator. The quantities of polyethylene glycol and aliphatic dibasic acid for each preparation are contained in Table II below. The reaction mixture was heated in the presence of 0.1 gram p-toluene sulfonic acid catalyst under a vacuum to a temperature of about 150 to 175 C. over a period of time of about 4 hours. Water was evaporated from the reaction mixture during the reaction period.
- the knitted sleeves were cut into fabric samples having a width of 2.5 inches and a length of 10 inches and the fabric samples were tested for their antistatic property TABLE H in accordance with the procedure described below.
- Polyethylene g y Dibasic acid A fabric sample was mounted on a grounded vertical l m w weight type 304 stainless steel frame and was stroked downward Prepammm weight E TYPB ten times with a stainless steel rod.
- the electrostatic volts oo 28 age on the fabric was measured by means of a Rothschild 1.200 3M4 Static Volt Meter, Model No. R-1019', positioned one lnch from the fabric which recorded the voltage on the fabric.
- the Field Half Time of the fabric was measured P 3 to determine the effectiveness of the various antistatic Antistatic agents of the present invention were preagents mlxed P Fleld Half pared in the following manner.
- Polyethylene glycol and T fi 9 the fabnc 1S defined as that P requlred for the an aliphatic dibasic acid were added with 10 ml. of dry 15 1n1t1al voltage measured on the fabr c to decrease to one Xylene to a 500 1 Rinco thin film evaporaton
- the quam half of its origlnal value The antistatic measurements 6 tities of polyethylene glycol and aliphatic dibasic acid e made immature of and a N for each preparation are contained in Table III below.
- Each of the batches of polyamide pellets containing an antistatic agent were melted at about 285 C. and then melt extruded under a pressure of 2,000 p.s.i.g. through a 14-orifice spinnerette, each of the orifices, haw'ng a diameter of 0.040 inch, to produce 820 denier fibers.
- the fibers were collected at about 1,500 feet per minute and were drawn about 4 times their extruded length to produce 210 denier yarns.
- a control yarn containing no antistatic agent was produced in the same manner as described above.
- Example 5 The 210 denier polycaproamide yarns containing an antistatic agent and the control yarn which were produced in Example 4 were knitted into sleeves. The yarns contained /zZ twist. The sleeves were then scoured in a conventional manner and dyed blue in an aqueous dye bath containing a Disperse Blue 3 dye using a conventional dyeing procedure.
- No'rE.Fabric samples A through E contained 3 weight percent of antistatic agent based upon the weight of the polyamide.
- the antistatic agents of the present invention are extremely effective in reducing the electrostatic charge on a fabric.
- the degree of polymerization of the antistatic agents of the present invention is generally between about 2 and 20, preferably between about 4 and 10.
- a filament, having antistatic properties comprised of a fiber forming polyamide having repeating carbonamide groups as an integral part of the polymeric chain mixed with about 2 to 5 weight percent, based on the weight of the polyamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid.
- a filament, having antistatic properties comprised of a polycaproamide mixed with about 2 to 5 weight percent, based on the weight of the polycaproamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000 and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid.
- a process for producing a filament, having antistatic properties comprised of fiber forming polyamide having repeating carbonamide groups as an integral part of the polymeric chain which comprises mixing said polyamide, prior to extrusion thereof, with about 2 to 5 weight percent, based on the weight of said polyamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid; and melt extruding the mixture of said fiber forming polymer and said reaction product to form a filament having antistatic properties.
- a process for producing a filament, having antistatic properties comprised of polycaproamide which comprises mixing said polycaproamide, prior to extrusion thereof, with about 2 to 5 weight percent, based on the weight of said polycaproamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid; and melt extruding the mixture of said fiber forming polymer and said reaction product to form a filament having antistatic properties.
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Abstract
A FILAMENT, HAVING ANTISTATIC PROPERTIES, COMPRISED OF A HYDROPHOBIC SYNTHETIC POLYMER HAVING MIXED THERETHROUGH ABOUT 1 TO 10 WEIGHT PERCENT, BASED ON THE WEIGHT OF THE HYDROPHOBIC SYNTHETIC POLYMER, OF THE REACTION PRODUCT OF A POLYGLYCOL WHICH CAN BE POLYETHYLENE GLYCOL OR A BLOCK COPOLYMER OF ETHYLENE OXIDE AND PROPYLENE OXIDE CONTAINING UP TO ABOUT 30 MOLE PERCENT PROPYLENE OXIDE, SAID POLYGLYCOL HAVING A MOLECULAR WEIGHT FROM ABOUT 100 TO 15,000 AND A COMPOUND WHICH HAS THE GENERAL FORMULA:
X-CO-(CH2)N-CO-X
WHEREIN X IS HYDROXYL,-OR WHEREIN R IS LOWER ALKYL, OR HALOGEN AND N IS AN INTEGER FROM 2 TO ABOUT 20.
X-CO-(CH2)N-CO-X
WHEREIN X IS HYDROXYL,-OR WHEREIN R IS LOWER ALKYL, OR HALOGEN AND N IS AN INTEGER FROM 2 TO ABOUT 20.
Description
United States Patent 3,655,821 POLYAMIDE FILAMENTS CONTAINING ANTI- STATIC POLYETHER PREPARED FROM A POLYALKYLENE AND AN ALIPHATIC DI- CARBOXYLIC ACID Robert A. Lofquist, Richmond, Va., and Brendan T. Hayes, deceased, late of Chester, Va., by Barbara E. Hayes, administratrix, Chester, Va., assignors to Allied Chemical Corporation, New York, N.Y. No Drawing. Filed Sept. 3, 1969, Ser. No. 855,469 Int. Cl. C08g 41/04 US. Cl. 260-857 PEG 4 Claims ABSTRACT OF THE DISCLOSURE A filament, having antistatic properties, comprised of a hydrophobic synthetic polymer having mixed therethrough about 1 to 10 weight percent, based on the weight of the hydrophobic synthetic polymer, of the reaction product of a polyglycol which can be polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 100 to 15,000 and a compound which has the general formula:
ll i XC(OH2)nCX wherein X is hydroxyl, -OR wherein. R is lower alkyl, or halogen and n is an integer from 2 to about 20.
BACKGROUND OF THE INVENTION This invention relates to compositions suitable for use in imparting antistatic properties to textile materials, to methods for preparing such compositions, to methods employing such compositions for decreasing the tendency of textiles to collect static charges and to textiles so produced.
Many textile fabrics, and particularly fabrics made of the recently developed synthetic yarns, display a marked tendency to collect static charges. This tendency is very objectionable in that it causes, in many instances, garments made therefrom to cling to the skin of the wearer in an undesirable manner. Garments made of such materials also tend to collect lint and fly and, in some instances, to drape in an undesirable manner.
There have previously been available many antistatic compositions which could be applied to yarns or fabrics which display a tendency to collect static charges but such compositions have been known, in most instances, to be easily removed by either washing or dry cleaning. This has limited the usefulness of these products primarily to manufacturing operations since the application of such products has been too expensive and involved to be undertaken by a dry cleaning establishment or laundry each time that garments made from such fabrics are cleaned. As a result, the wearer of garments woven from materials which tend to collect static electricity has been forced to tolerate this undesirable characteristic throughout substantially the entire life of the garments.
Some antistatic agents have been found resistant to Washing or dry cleaning but they impart a harsh hand to yarns and fabrics or adversely affect the dyeability of the yarns and fabrics.
It has now been discovered that the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof is an effective antistatic agent which can be mixed with a hydrophobic synthetic polymer prior to the extrusion of the synthetic polymer into a filament. The mixture of the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof throughout the hydrophobic synthetic filament produces yarns and fabrics containing the filaments which have excellent antistatic properties. Furthermore, the antistatic agents of the present invention resist Washing and dry cleaning since they are mixed throughout the filaments and do not impart a harsh hand to the yarns and fabrics. Finally, the antistatic agents of the present invention do not significantly affect the dyeability of the yarns and fabrics.
SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a filament, having antistatic properties comprised of a hydrophobic synthetic polymer having mixed therethrough about 1 to 10, preferably about 2 to 5, percent, based on the weight of the hydrophobic synthetic polymer, of the reaction product of a polyglycol which can be polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about to 15,000, preferably about 200' to 10,000, and a compound which has the general formula:
wherein X is hydroxyl, OR wherein R is lower al=kyl, or halogen such as chlorine or bromine and n is an integer from 2 to about 20, preferably 2 to about 10.
DESCRIPTION OF THE INVENTION The filament-forming hydrophobic synthetic polymer can be a polyolefin, polysulfone, polyphenyl oxide, polycarbonate, polyacrylonitrile, polyamide, polyester and the like or polymer blends thereof. Examples of suitable polymer blends as disclosed above are dispersions of polyester in polyamide such as disclosed in US. Pat. 3,369,057 to Twilley; US. Pats. 3,378,055, 3,378,056, and 3,378,602; British Pat. 1,097,068; Belgian Pat. 702,813; and Netherlands Pats. 6606838 and 6612628. The filament of the present invention can be prepared from these dispersions by known melt spinning techniques.
In a preferred embodiment of the present invention, the filament-forming synthetic polymer is a polyamide or a polyester. The filament of the present invention can be prepared from these polymers by known melt spinning techniques.
Suitable polyamides for use in the present invention include, for example, those prepared by condensation of hexamethylene diamine and adipic acid, condensation of hexamethylene diamine and sebacic acid known as nylon 6,6 and nylon 6,10, respectively, condensation of his (para-aminocyclohexyl)methane and azelaic acid, condensation of bis(paraaminocyclohexyl)methane and dodecanedioic acid, or by polymerization of 6-caprolactam, 7-aminoheptanoic acid, 8-caprylactam, 9-arninopelargonic acid, ll-aminoundecanoic acid, and 12-dodecalactam, known as nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, and nylon 12, respectively.
The polyesters useful in the practice of this invention can be prepared in general by condensation reactions between dicarboxylic acids or their derivatives and compounds containing two hydroxyl groups, or materials possessing both an alcohol group and a carboxylic acid group or derivative thereof; or by polymerization of lactones. Dicarboxylic acid derivatives which can be employed include esters, salts, anhydrides and acid halides. The monomeric species employed in the preparation of the polyesters are preferably not more highly functional than difunctional in their reactivity so as to produce essentially linear, non-crosslinked polymer structures.
Suitable polyesters for use in the present invention include those polymers in which one of the recurring units in the polyester chain is the diacylaromatic radical from terephthalic acid, isophthalic acid, S-t-butylisophthalic acid, a naphthalene dicarboxylic acid such as naphthalene 2,6 and 2,7 dicarboxylic acids, a diphenyl dicarboxylic acid, a diphenyl ether dicarboxylic acid, a diphenyl alkylene dicarboxylic acid, a diphenyl sulphone dicarboxylic acid, an azo dibenzoic acid, a pyridine dicarboxylic acid, a quinoline dicarboxylic acid, and analogous aromatic species including the sulfonic acid analogues, diacyl radicals containing cyclopentane or cyclohexane rings between the acyl groups; and such radicals substituted in the ring, e.g., by alkyl or halo substituents.
The dioxy radical representing the other principal recurring unit in the polyester chain can be an open chain aliphatic such as ethylene glycol or ether thereof, for example, the diether, or can contain rings such as those which form part of the above noted diacyl radicals. The carboxy and/or the oxy chain members can be directly attached to a ring or removed by one or more carbons therefrom, as in the 1,4 dioxymethyl cyclohexane radical.
The preferred polyester is poly( ethylene terephthalate) Other suitable polyesters include poly(dimethylene cyclohexylene terephthalate) and poly(4-ethoxy benzoate).
The antistatic agent of the present invention is the reaction product of a polyglycol and an aliphatic dibasic acid or a derivative thereof.
Suitable polyglycols include polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide. The polyglycol can have a molecular weight from about 100 to 15,000, preferably about 200 to 10,000.
Suitable compounds having the formula X-iJ-(OHM-i'J-X wherein X and n are defined above include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, pimelic acid and their corresponding acid halides such as chlorides and bromides and their lower alkyl esters. The (CH divalent radical in the above formula can be substituted with nonreactive groups such as p-phenylene, m-phenylene, and p-xylylene.
The antistatic agents of the present invention can be prepared by any of the known methods. A typical method comprises charging into a flask, equipped with a heater, stirrer, reflux condenser and a thermometer, a polyethylene glycol having a molecular weight from about 100 to 15,000, preferably about 200 to 10,000; a compound which has the general formula:
wherein X is hydroxyl, --OR wherein R is lower alkyl, or halogen such as chlorine or bromine and n is an integer from 2 to about 20, preferably 2 to about and an inert solvent, such as dry xylene. The reaction mixture can then be heated to the boiling temperature of the reaction mixture and be reacted while refluxing in the presence of a catalytic amount of a suitable esterification catalyst such as p-toluene sulfonic acid or sulfuric acid. The above reaction is usually carried out for a period of about 2 to 8 hours. At the end of the above reaction period, the reflux condenser can be replaced by a moisture trap and refluxing of the reaction mixture can be continued until no additional water appears in the moisture trap. The reaction mixture can then be cooled below its boiling temperature and the reaction flask can be set up to distill off the inert solvent. The distillation temperature should not be allowed to exceed about 150 to 175 C. and the inert solvent should not be distilled at a rate greater than about 2 to 4 ml. per minute. When most of the inert solvent is removed, the reaction mixture can then be transferred to a thin film evaporator and the reaction mixture heated to a temperature of about 150 to 175 C. under a vacuum of about 1 to 10 mm. of mercury for a 4 period of time of about 2 to 6 hours or until no more volatiles can be removed.
Under certain circumstances, the reaction mixture can be reacted in the thin film evaporator in the presence of little or no inert solvent as shown in Examples 2 and 3.
In general, it has been found desirable to prepare the antistatic agents by heating together one molecular portion of the polyglycol with from about 1.0 to 1.1 molecular portions of the dibasic acid. It is preferred that enough excess dibasic acid be added so that both ends of the antistatic agent have carboxyl end groups.
Generally speaking, about 1 to 10 weight percent of the antistatic agent, based upon the weight of the synthetic polymer, will produce the desired antistatic properties in the filament, however, it is preferred that about 2 to 5 weight percent be used.
The antistatic agent can be mixed with the synthetic polymer during the polymerization, preferably at the end of the polymerization, of the synthetic polymer or can be mixed into the molten synthetic polymer by, for example, injection into the mixing portion of the extruder prior to the melt extrusion of the filament. Alternatively, the antistatic agent can be blended with the synthetic polymer granules prior to the melting of the synthetic polymer by conventional addition and mixing procedures.
PREFERRED EMBODIMENTS The following examples illustrate the practice and principles of this invention and a mode of carrying out the invention.
Example 1 Antistatic agents of the present invention were prepared in the following manner. Polyethylene glycol and an aliphatic dibasic acid were added to a one liter flask containing 500 ml. of dry xylene. The quantities of polyethylene glycol and aliphatic dibasic acid for each preparation are contained in Table I below. The one liter flask was equipped with a heater, stirrer, reflux condenser and a thermometer. The reaction mixture was heated to the boiling temperature of the reaction mixture and reacted while refluxing was in the presence of 0.1 gram p-toluene sulfonic acid catalyst at the boiling temperature of the reaction mixture for one hour. At the end of the one hour reaction period, the reflux condenser was replaced by a Dean-Stark trap and refluxing of the reaction mixture was continued until no additional water appeared in the Dean- Stark trap. The reaction mixture was then cooled below its boiling temperature and the reaction flask was set up to distill oil? the xylene. The distillation temperature was not allowed to exceed C. and the xylene was distilled at a rate no greater than 10 ml. per minute. When most of the xylene was removed, the reaction mixture was then transferred to a 500 ml. Rinco thin film evaporator and the reaction mixture was heated to a temperature of about 150 to C. under a vacuum of about 2 mm. Hg until no more volatiles could be removed.
TABLE I Polyethylene glycol Dlbasic acid Molecular Wei ht Wei ht Preparation No. weight gins. Type gins:
400 200 Sebaeic 103.12 1,200 200 do 34.37 6,000 200 do 6. 87
Example 2 Antistatic agents of the present invention were prepared in the following manner. Polyethylene glycol and an aliphatic dibasic acid were added to a 500 ml. Rinco thin film evaporator. The quantities of polyethylene glycol and aliphatic dibasic acid for each preparation are contained in Table II below. The reaction mixture was heated in the presence of 0.1 gram p-toluene sulfonic acid catalyst under a vacuum to a temperature of about 150 to 175 C. over a period of time of about 4 hours. Water was evaporated from the reaction mixture during the reaction period.
The knitted sleeves were cut into fabric samples having a width of 2.5 inches and a length of 10 inches and the fabric samples were tested for their antistatic property TABLE H in accordance with the procedure described below. Polyethylene g y Dibasic acid A fabric sample was mounted on a grounded vertical l m w weight type 304 stainless steel frame and was stroked downward Prepammm weight E TYPB ten times with a stainless steel rod. The electrostatic volts oo 28 age on the fabric was measured by means of a Rothschild 1.200 3M4 Static Volt Meter, Model No. R-1019', positioned one lnch from the fabric which recorded the voltage on the fabric. The Field Half Time of the fabric was measured P 3 to determine the effectiveness of the various antistatic Antistatic agents of the present invention were preagents mlxed P Fleld Half pared in the following manner. Polyethylene glycol and T fi 9 the fabnc 1S defined as that P requlred for the an aliphatic dibasic acid were added with 10 ml. of dry 15 1n1t1al voltage measured on the fabr c to decrease to one Xylene to a 500 1 Rinco thin film evaporaton The quam half of its origlnal value. The antistatic measurements 6 tities of polyethylene glycol and aliphatic dibasic acid e made immature of and a N for each preparation are contained in Table III below. relatlve humldlty of results P h annstatlc The d mixture was hgated infthe presence f Q1 measurements of the fabrics are contained in Table IV gram-p-toluene sulfonic acid catalyst under a vacuum to belowa temperature of about 180 to 200 C. over a period of TABLE IV time of about hours. Water and xylene were evaporated Antistatic agent reactants from the reaction mixture during the reaction period. 1 th I 0 6 TABLE III ene glyebl, molecular Polyethylene glycol Dibasie acid Fabric sample weight Molecular Weight, Weight, Preparation No. weight gins. Type gms. 1 :38 i o 400 200 Succinic- 59.1 1000 5 H 1, 200 204 .-...do 20.84 6,000 14 1,200 5 238 s 3 110011110- Example 4 1,200 6 A series of glass reactors each equipped with a heater and stirrer were charged with a mixture of 1520 grams of e-caprolactam and 80 grams of aminocaproic acid. The mixture were then flushed with nitrogen and were stirred and heated to 255 C. over a one hour period at atmosperic pressure to produce polymerization reactions. The heating and stirring were continued at atmospheric pressure under a nitrogen sweep for an additional fourteen hours in order to complete the polymerizations. During the last thirty minutes of each polymerization, 48 grams of antistatic agent A, B, C, D, E, F, G, or H as prepared in Examples 1, 2 and 3 was respectively added to one of the polycaproamide polymerization batches and stirring was continued to thoroughly mix each antistatic agent throughout the polymers. Nitrogen was then admitted to the glass reactors and a small pressure was maintained while the polymers were extruded from the glass reactors in the form of polymer ribbons. The polymer ribbons were subsequently cooled, pelleti'zed using a Wiley Mill, washed and then dried. The polymers were white solids having relative viscosities of about 50, as determined at a concentration of 11 grams of polymer in 100 ml. of 90 percent formic acid at 25 C. (ASTM D-789- 62T).
Each of the batches of polyamide pellets containing an antistatic agent were melted at about 285 C. and then melt extruded under a pressure of 2,000 p.s.i.g. through a 14-orifice spinnerette, each of the orifices, haw'ng a diameter of 0.040 inch, to produce 820 denier fibers. The fibers were collected at about 1,500 feet per minute and were drawn about 4 times their extruded length to produce 210 denier yarns. A control yarn containing no antistatic agent was produced in the same manner as described above.
' Example 5 The 210 denier polycaproamide yarns containing an antistatic agent and the control yarn which were produced in Example 4 were knitted into sleeves. The yarns contained /zZ twist. The sleeves were then scoured in a conventional manner and dyed blue in an aqueous dye bath containing a Disperse Blue 3 dye using a conventional dyeing procedure.
No'rE.Fabric samples A through E contained 3 weight percent of antistatic agent based upon the weight of the polyamide.
As can be seen from the data contained in Table IV above, the antistatic agents of the present invention are extremely effective in reducing the electrostatic charge on a fabric.
The degree of polymerization of the antistatic agents of the present invention is generally between about 2 and 20, preferably between about 4 and 10.
[[t is claimed:
1. A filament, having antistatic properties, comprised of a fiber forming polyamide having repeating carbonamide groups as an integral part of the polymeric chain mixed with about 2 to 5 weight percent, based on the weight of the polyamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid.
2. A filament, having antistatic properties, comprised of a polycaproamide mixed with about 2 to 5 weight percent, based on the weight of the polycaproamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000 and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid.
3. A process for producing a filament, having antistatic properties, comprised of fiber forming polyamide having repeating carbonamide groups as an integral part of the polymeric chain which comprises mixing said polyamide, prior to extrusion thereof, with about 2 to 5 weight percent, based on the weight of said polyamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid; and melt extruding the mixture of said fiber forming polymer and said reaction product to form a filament having antistatic properties.
4. A process for producing a filament, having antistatic properties, comprised of polycaproamide which comprises mixing said polycaproamide, prior to extrusion thereof, with about 2 to 5 weight percent, based on the weight of said polycaproamide, of the reaction product consisting essentially of a polyglycol selected from the group consisting of polyethylene glycol and block copolymers of ethylene oxide and propylene oxide containing up to about 30 mole percent propylene oxide, said polyglycol having a molecular weight from about 200 to 10,000, and a compound selected from the group consisting of succinic acid, sebacic acid and dodecanedioic acid; and melt extruding the mixture of said fiber forming polymer and said reaction product to form a filament having antistatic properties.
References Cited UNITED STATES PATENTS 4/1968 Senoo et a1. 260860 11/ 1968 Crovatt 260-860 5/ 1969 Bonin 260-860 12/ 197 0 East '260857 12/ 1970 Okazaki 260--857 12/1970 Ogata 260-857 I/ 1971 Bonnard 260-860 4/1971 Kimura et al. 260-857 PEO FOREIGN PATENTS 5/ 1967 France. 1/1968 Netherlands.
1964 Japan. 1965 Japan.
PAUL LIEBERMAN, Primary Examiner US. Cl. X.R.
260-823, 857 PE, 860, 897 R, 898
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US85546969A | 1969-09-03 | 1969-09-03 |
Publications (1)
Publication Number | Publication Date |
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US3655821A true US3655821A (en) | 1972-04-11 |
Family
ID=25321334
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US855469A Expired - Lifetime US3655821A (en) | 1969-09-03 | 1969-09-03 | Polyamide filaments containing antistatic polyether prepared from a polyalkylene and an aliphatic dicarboxylic acid |
Country Status (1)
Country | Link |
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US (1) | US3655821A (en) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839245A (en) * | 1972-03-30 | 1974-10-01 | Emery Industries Inc | Poly(ether-ester-amide) antistatic compositions derived from dimr acids |
US3860671A (en) * | 1973-03-29 | 1975-01-14 | Akzona Inc | Polyamide fibers with improved antistatic effect and their preparation |
US3944629A (en) * | 1974-06-24 | 1976-03-16 | Monsanto Company | Polyester initiated anionic catalyzed polymerization of lactam |
US3993709A (en) * | 1974-06-24 | 1976-11-23 | Monsanto Company | Polyester initiated anionic catalyzed polymerization of lactam |
US4032595A (en) * | 1973-01-12 | 1977-06-28 | Imperial Chemical Industries Limited | Antistatic agents |
US4035341A (en) * | 1971-05-24 | 1977-07-12 | Rhone-Poulenc-Textile | Polyester compositions with good dyeing affinity and a process for obtaining same |
US4051196A (en) * | 1975-05-27 | 1977-09-27 | Allied Chemical Corporation | Antistatic fiber containing chain-extended tetrols based on diamines |
US4128525A (en) * | 1974-11-29 | 1978-12-05 | Texaco Development Corp. | Thermoplastic adhesives |
US4165303A (en) * | 1974-01-16 | 1979-08-21 | Emery Industries, Inc. | Polymer compositions containing poly (alkylene ether) esters of polybasic acids |
US4182845A (en) * | 1974-11-29 | 1980-01-08 | Texaco Development Corporation | Preparation of polyamide thermoplastic adhesive from polyoxypropylene polyamine and piperazine |
US4207410A (en) * | 1977-03-24 | 1980-06-10 | Chemische Werke Huls Aktiengesellschaft | Method for the preparation and use of polyether ester amides with units of the starting components randomly distributed in the polymer chain |
US4234184A (en) * | 1978-02-24 | 1980-11-18 | Ato Chimie | Thermoplastic polymer cover for golf balls and golf balls comprising such a cover |
US4252920A (en) * | 1977-09-02 | 1981-02-24 | Ato Chimie | Method for preparing ether-ester-amide block polymers for among other moulding, extruding or spinning uses |
US4328331A (en) * | 1981-04-20 | 1982-05-04 | The Upjohn Company | Novel polyester-amides |
US4346024A (en) * | 1979-12-10 | 1982-08-24 | Rhone-Poulenc Industries | Heat-stable polyphase polyamide/polyesteramide compositions |
US4346200A (en) * | 1980-12-29 | 1982-08-24 | Monsanto Company | Thermoplastic polyamide compositions |
US4379913A (en) * | 1982-05-04 | 1983-04-12 | Diamond Shamrock Corporation | Compositions useful as internal antistatic additives for polymeric structures |
US4468433A (en) * | 1982-07-26 | 1984-08-28 | E. I. Du Pont De Nemours And Company | Antistatic composition and polyester fiber containing same |
US4506070A (en) * | 1982-07-26 | 1985-03-19 | E. I. Du Pont De Nemours And Company | Antistatic composition and polyester fiber containing same |
JPS60133022A (en) * | 1983-12-20 | 1985-07-16 | Osaka Suiso Kogyo Kk | Polycondensation product |
JPS6197244A (en) * | 1984-10-16 | 1986-05-15 | Osaka Suiso Kogyo Kk | Polycondensate |
US5194319A (en) * | 1988-03-07 | 1993-03-16 | Kanebo, Ltd. | Shaped polyamide articles and process for manufacturing the same |
US5321068A (en) * | 1992-11-24 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Fiber of polyadipamide polymer containing added succinic acid |
-
1969
- 1969-09-03 US US855469A patent/US3655821A/en not_active Expired - Lifetime
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4035341A (en) * | 1971-05-24 | 1977-07-12 | Rhone-Poulenc-Textile | Polyester compositions with good dyeing affinity and a process for obtaining same |
US3839245A (en) * | 1972-03-30 | 1974-10-01 | Emery Industries Inc | Poly(ether-ester-amide) antistatic compositions derived from dimr acids |
US4032595A (en) * | 1973-01-12 | 1977-06-28 | Imperial Chemical Industries Limited | Antistatic agents |
US3860671A (en) * | 1973-03-29 | 1975-01-14 | Akzona Inc | Polyamide fibers with improved antistatic effect and their preparation |
US4165303A (en) * | 1974-01-16 | 1979-08-21 | Emery Industries, Inc. | Polymer compositions containing poly (alkylene ether) esters of polybasic acids |
US3944629A (en) * | 1974-06-24 | 1976-03-16 | Monsanto Company | Polyester initiated anionic catalyzed polymerization of lactam |
US3993709A (en) * | 1974-06-24 | 1976-11-23 | Monsanto Company | Polyester initiated anionic catalyzed polymerization of lactam |
US4128525A (en) * | 1974-11-29 | 1978-12-05 | Texaco Development Corp. | Thermoplastic adhesives |
US4182845A (en) * | 1974-11-29 | 1980-01-08 | Texaco Development Corporation | Preparation of polyamide thermoplastic adhesive from polyoxypropylene polyamine and piperazine |
US4051196A (en) * | 1975-05-27 | 1977-09-27 | Allied Chemical Corporation | Antistatic fiber containing chain-extended tetrols based on diamines |
US4207410A (en) * | 1977-03-24 | 1980-06-10 | Chemische Werke Huls Aktiengesellschaft | Method for the preparation and use of polyether ester amides with units of the starting components randomly distributed in the polymer chain |
US4252920A (en) * | 1977-09-02 | 1981-02-24 | Ato Chimie | Method for preparing ether-ester-amide block polymers for among other moulding, extruding or spinning uses |
US4234184A (en) * | 1978-02-24 | 1980-11-18 | Ato Chimie | Thermoplastic polymer cover for golf balls and golf balls comprising such a cover |
US4346024A (en) * | 1979-12-10 | 1982-08-24 | Rhone-Poulenc Industries | Heat-stable polyphase polyamide/polyesteramide compositions |
US4346200A (en) * | 1980-12-29 | 1982-08-24 | Monsanto Company | Thermoplastic polyamide compositions |
US4328331A (en) * | 1981-04-20 | 1982-05-04 | The Upjohn Company | Novel polyester-amides |
US4379913A (en) * | 1982-05-04 | 1983-04-12 | Diamond Shamrock Corporation | Compositions useful as internal antistatic additives for polymeric structures |
US4468433A (en) * | 1982-07-26 | 1984-08-28 | E. I. Du Pont De Nemours And Company | Antistatic composition and polyester fiber containing same |
US4506070A (en) * | 1982-07-26 | 1985-03-19 | E. I. Du Pont De Nemours And Company | Antistatic composition and polyester fiber containing same |
JPS60133022A (en) * | 1983-12-20 | 1985-07-16 | Osaka Suiso Kogyo Kk | Polycondensation product |
JPS6197244A (en) * | 1984-10-16 | 1986-05-15 | Osaka Suiso Kogyo Kk | Polycondensate |
US5194319A (en) * | 1988-03-07 | 1993-03-16 | Kanebo, Ltd. | Shaped polyamide articles and process for manufacturing the same |
US5321068A (en) * | 1992-11-24 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Fiber of polyadipamide polymer containing added succinic acid |
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