NO140856B - ANALOGICAL PROCEDURE FOR THE PREPARATION OF ALKYL SULPHONYLPHENOXY-PROPANOLAMINE COMPOUNDS - Google Patents
ANALOGICAL PROCEDURE FOR THE PREPARATION OF ALKYL SULPHONYLPHENOXY-PROPANOLAMINE COMPOUNDS Download PDFInfo
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- NO140856B NO140856B NO750993A NO750993A NO140856B NO 140856 B NO140856 B NO 140856B NO 750993 A NO750993 A NO 750993A NO 750993 A NO750993 A NO 750993A NO 140856 B NO140856 B NO 140856B
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- Prior art keywords
- acid
- alkyl
- yarn
- diamine
- forming
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 17
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims description 8
- 239000000980 acid dye Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- -1 diamine salt Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 description 26
- 229920002647 polyamide Polymers 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000000975 dye Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-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
- 239000011707 mineral Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-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
- 238000006116 polymerization reaction Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- KYANBEHLJRQXNU-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-2,4-diene-1-sulfonic acid Chemical compound CC1=CC(C)=CC(C)(S(O)(=O)=O)C1 KYANBEHLJRQXNU-UHFFFAOYSA-N 0.000 description 1
- NVDLBTXSGQWRSH-UHFFFAOYSA-N 1,4,5,6-tetramethylcyclohexa-2,4-diene-1-sulfonic acid Chemical compound CC1(C(C(=C(C=C1)C)C)C)S(=O)(=O)O NVDLBTXSGQWRSH-UHFFFAOYSA-N 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-N 1,6-dimethylcyclohexa-2,4-diene-1-sulfonic acid Chemical compound CC1C=CC=CC1(C)S(O)(=O)=O GDJZZWYLFXAGFH-UHFFFAOYSA-N 0.000 description 1
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-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
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ZQGPVVNVISOGEU-UHFFFAOYSA-N 2-propylbenzenesulfonic acid Chemical compound CCCC1=CC=CC=C1S(O)(=O)=O ZQGPVVNVISOGEU-UHFFFAOYSA-N 0.000 description 1
- HYZYOKHLDUXUQK-UHFFFAOYSA-N 3-methylbutane-1-sulfonic acid Chemical compound CC(C)CCS(O)(=O)=O HYZYOKHLDUXUQK-UHFFFAOYSA-N 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
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical group 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AKRQHOWXVSDJEF-UHFFFAOYSA-N heptane-1-sulfonic acid Chemical compound CCCCCCCS(O)(=O)=O AKRQHOWXVSDJEF-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical class NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte til fremstilling av fiberdannende poiycarbonamider som er mottagelige for sure farvestoffer. Process for the production of fiber-forming polycarbonamides which are receptive to acid dyes.
Denne oppfinnelse vedrører fremstilling av modifiserte syntetiske lineære poiycarbonamider som har en øket mottagelighet for sure farvestoffer. This invention relates to the production of modified synthetic linear polycarbonamides which have an increased susceptibility to acid dyes.
De polymere stoffer som denne oppfinnelsen vedrører, er syntetiske, høymo-lekylære, fiberdannende poiycarbonamider av den type som kjennetegnes ved tilstede-værelse av tilbakevendende carbonamid-grupper som utgjør en integrerende del av The polymeric substances to which this invention relates are synthetic, high-molecular, fiber-forming polycarbonamides of the type characterized by the presence of recurring carbonamide groups which form an integral part of
polymerisatkjeden og som er adskilt ved the polymer chain and which are separated by
minst to carbonatomer. De utmerker seg at least two carbon atoms. They excel
dessuten ved høyt smeltepunkt, fremtre-dende krystallinitet og er uoppløselige i de moreover, at a high melting point, prominent crystallinity and are insoluble in them
fleste oppløsningsmidler unntagen i mineralsyrer, maursyre og fenoler. Ved hydro-lyse med sterke mineralsyrer spaltes polymerisatene til de utgangsforbindelser hvor-av de er dannet. most solvents except in mineral acids, formic acid and phenols. During hydrolysis with strong mineral acids, the polymers are split into the starting compounds from which they are formed.
De enkle polyamider av denne type The simple polyamides of this type
fremstilles vanligvis ved å opphete hoved-sakelig ekvimolare mengder av en diamin is usually prepared by heating mainly equimolar amounts of a diamine
med en dicarboxylsyre inntil produktet er with a dicarboxylic acid until the product is
blitt polymerisert til det fiberdannende been polymerized into the fiber-forming
trinn. Dette trinn nåes vanligvis ikke før steps. This step is usually not reached before
polyamidet har nådd en grenseviskositet the polyamide has reached a limiting viscosity
på minst 0,4 dl/g. Grenseviskositeten defi-neres som følger: of at least 0.4 dl/g. The limiting viscosity is defined as follows:
Den uttrykkes i deciliter pr. gram, dvs. det It is expressed in deciliters per grams, i.e. it
inverse av konsentrasjonsenhetene. Denne inverse of the concentration units. This
bestemmelse av grenseviskositeten er helt determination of the limiting viscosity is completely
teoretisk da c nærmer seg 0 og konsent-rasjonen av et polymerisat selvsagt aldri kan bli absolutt lik 0. 2 sp er den spesifikke viskositet av en fortynnet oppløsning av polymerisatet i m-cresol idet de sistnevn-te er uttrykt i de samme enheter ved samme temperatur, og c betegner konsentra-sjonen uttrykt i gram polymerisat pr. deciliter oppløsning. theoretically as c approaches 0 and the concentration of a polymer can of course never be absolutely equal to 0. 2 sp is the specific viscosity of a dilute solution of the polymer in m-cresol, the latter being expressed in the same units at the same temperature, and c denotes the concentration expressed in grams of polymer per deciliter solution.
Den spesifikke viskositet som her anvendt, uttrykkes ved formelen: The specific viscosity used here is expressed by the formula:
Viskositetsmålinger for de polymere opp-løsninger og for oppløsningsmidlet utføres ved at de nevnte oppløsninger får strømme ved 25°C under innvirkning av tyngdekraf-ten gjennom et kapillært viskositetsrør. Ved bestemmelsen av de spesifikke viskosi-teter ble der anvendt polymere oppløsnin-ger inneholdende 0,5 vektspst. av polymerisatene oppløst i et oppløsningsmiddel som ovenfor beskrevet. Viscosity measurements for the polymeric solutions and for the solvent are carried out by allowing the aforementioned solutions to flow at 25°C under the influence of gravity through a capillary viscosity tube. When determining the specific viscosities, polymeric solutions containing 0.5% by weight were used. of the polymers dissolved in a solvent as described above.
Diaminene og dicarboxylsyrene som kan anvendes som reaktanter fører til de vel kjente enkle fiberdannende polyamider. Egnede diaminer kan representeres ved den generelle formel NH2[CH2]nNH2, hvori n er et helt tall 2 eller større, fortrinnsvis fra 2 til 10. Karakteristiske eksempler er ethylendiamin, propylendiamin, tetramet-hylendiamin, pentamethylendiamin, hexamethylendiamin, oktamethylendiamin og dekamethylendiamin. Anvendbare dicarbo-xylsyrer er representert ved den generelle formel HOOCRCOOH, hvori R er divalent hydrocarbon-radikal med en kjedelengde på minst to carbonatomer. Disse dicarbo-xylsyrer illustreres ved sebacinsyre, okta-dekandi-syre, adipinsyre, suberinsyre, aze-lansyre, undekandisyre, glutarinsyre, pime-linsyre, brassylinsyre og tetradekandisyre. Diaminers amiddannende derivater som kan anvendes, omfatter carbamat- og N-formyl-derivatene. Amiddannende derivater av de tobasiske carboxylsyrer som også er anvendbare, er mono- og diesterene, an-hydridene, mono- og diamidene og de sure halogenider. The diamines and dicarboxylic acids that can be used as reactants lead to the well-known simple fiber-forming polyamides. Suitable diamines can be represented by the general formula NH2[CH2]nNH2, in which n is an integer 2 or greater, preferably from 2 to 10. Characteristic examples are ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine and decamethylenediamine. Useful dicarboxylic acids are represented by the general formula HOOCRCOOH, in which R is divalent hydrocarbon radical with a chain length of at least two carbon atoms. These dicarboxylic acids are illustrated by sebacic acid, octadecanoic acid, adipic acid, suberic acid, azelaic acid, undecanoic acid, glutaric acid, pimelic acid, brassylic acid and tetradecanoic acid. Amide-forming derivatives of diamines which can be used include the carbamate and N-formyl derivatives. Amide-forming derivatives of the dibasic carboxylic acids which are also useful are the mono- and diesters, the anhydrides, the mono- and diamides and the acid halides.
Mens det er kjent at tekstiler som er fremstillet av de forannevnte polyamider, har endel affinitet til sure farvestoffer, er det ikke nok til å foreta dypskyggefarvning. Dessuten er farveopptagningshastigheten forholdsvis liten og begrenser produktivite-ten ved fabrikasjonen av farvede tøyer og andre farvede artikler. While it is known that textiles made from the aforementioned polyamides have a certain affinity for acid dyes, it is not enough to carry out deep shade dyeing. In addition, the rate of color uptake is relatively small and limits productivity in the manufacture of colored cloth and other colored articles.
Der er tidligere gjort forsøk på å for-bedre farveegenskaper hos polyamidfibre og -tøyer ved å behandle dem med forskjellige midler. Den kjemiske behandling av et allerede dannet polymerisat-produkt kan imidlertid bare lette farveabsorpsjonen, den øker ikke polymerisatets iboende evne til å oppta farvestoff. Dessuten kreves der vanligvis store mengder behandlingsmid-ler, nemlig ofte så meget som 10 pst. Derfor har man lenge søkt å finne bedre metoder til å øke polyamidfibres og -tøyers far-vemottagelighet, især hva angår disse po-lymerisaters mulighet for å absorbere store mengder sure farvestoffer. Attempts have previously been made to improve the color properties of polyamide fibers and fabrics by treating them with various agents. However, the chemical treatment of an already formed polymer product can only facilitate dye absorption, it does not increase the inherent ability of the polymer to absorb dye. In addition, large amounts of treatment agents are usually required, namely often as much as 10 percent. Therefore, people have long sought to find better methods to increase the color acceptability of polyamide fibers and fabrics, especially with regard to the ability of these polymers to absorb large amounts of acid dyes.
Det er derfor et hovedformål ved nærværende oppfinnelse å fremstille lineære polyamider som kan farves i dype toner ved hjelp av sure f arvestoff typer. It is therefore a main purpose of the present invention to produce linear polyamides which can be dyed in deep tones using acidic dye types.
Eet annet formål er å fremstille syntetiske lineære polyamider som vil absorbere farvestoffer med en øket hastighet. Another purpose is to produce synthetic linear polyamides that will absorb dyes at an increased rate.
Ifølge oppfinnelsen fremstilles fiberdannende lineære poiycarbonamider med forbedret mottagelighet for sure farvestoffer hvorved man polymeriserer praktisk talt ekvimolare mengder av en dicarboxylsyre og et diamin, fortrinnsvis adipinsyre og hexamethylendiamin. Det karakteristiske hovedtrekk ved fremgangsmåten ifølge kra-vet består i at nevnte forbindelser sampolymeriseres med fra 0,35 til 14,0 mol-pst. av en sulfonsyre med den generelle formel- According to the invention, fiber-forming linear polycarbonamides are produced with improved receptivity to acid dyes, whereby practically equimolar amounts of a dicarboxylic acid and a diamine, preferably adipic acid and hexamethylenediamine, are polymerized. The characteristic main feature of the method according to the claim is that said compounds are copolymerized with from 0.35 to 14.0 mole percent. of a sulfonic acid with the general formula-
(i hvilken R er et hydrocarbonradikal med (in which R is a hydrocarbon radical with
fra 1 til 26 carbonatomer valgt blant alkyl-grupper, monoarylsubstituerte- og alkyl-substituerte monoarylgrupper), eller et diaminsalt av en sulfonsyre som angitt. from 1 to 26 carbon atoms selected from alkyl groups, monoaryl-substituted and alkyl-substituted monoaryl groups), or a diamine salt of a sulfonic acid as indicated.
Eksempler på sulfonsyrer som faller inn under den generelle formels område og som egner seg for oppfinnelsens øyemed, er fenylsulfonsyre, p-toluensulfonsyre, o-toluensulfonsyre, n-propylfenylsulfonsyre, p-isopropylfenylsulfonsyre, 1,3,5-trimethyl-f enylsulf onsyre, 1,2,3,4-tetramethylf enyl-sulfonsyre, l-methyl-4-isopropylfenylsulfonsyre, o-xylensulfonsyre, methansulfon-syre, etansulfonsyre, heptansulfonsyre, 3-methylbutan-1 -sulfonsyre, propan-1 -sulfonsyre, n-oktandekylsulfonsyre, n-dekyl-sulfonsyre, etc. Examples of sulfonic acids that fall under the scope of the general formula and which are suitable for the purpose of the invention are phenylsulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, n-propylphenylsulfonic acid, p-isopropylphenylsulfonic acid, 1,3,5-trimethyl-phenylsulfonic acid, 1,2,3,4-tetramethylphenylsulfonic acid, l-methyl-4-isopropylphenylsulfonic acid, o-xylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, heptanesulfonic acid, 3-methylbutane-1-sulfonic acid, propane-1-sulfonic acid, n-octanedecylsulfonic acid , n-decyl sulfonic acid, etc.
Der er blitt antydet at diaminsaltene av de forannevnte sulfonsyrer også kan brukes. Disse salter kan oppnåes på den vanlige måte ved omsetning av ekvivalente vektmengder av den valgte sulfonsyre med et passende diamin. De diaminer som kan anvendes ved dannelse av de forannevnte salter, kan være et hvilket som helst av de som er nevnt som anvendelige til fremstilling av fiberdannende polyamider, dvs. de diaminer som kan representeres av den generelle formel NH2[CH2]nNH2, hvori n er et helt tall 2 eller større og fortrinnsvis fra 2 til 10. Blant spesielle eksempler som kan nevnes, er pentamethylendiamin, hexamethylendiamin, oktamethylendiamin og dekamethylendiamin. Det diamin som anvendes til å danne det sulfonsure salt, kan være det samme som eller forskjellig fra det man anvender til å danne polyamid-saltet. Det samme eller forskjellige diaminer kan altså være tilstede ved dannelse av polymerisatene ifølge oppfinnelsen. It has been suggested that the diamine salts of the aforementioned sulphonic acids can also be used. These salts can be obtained in the usual way by reacting equivalent amounts by weight of the selected sulphonic acid with a suitable diamine. The diamines which can be used in the formation of the above-mentioned salts can be any of those mentioned as applicable to the production of fibre-forming polyamides, i.e. the diamines which can be represented by the general formula NH2[CH2]nNH2, in which n is an integer of 2 or greater and preferably from 2 to 10. Among particular examples that may be mentioned are pentamethylenediamine, hexamethylenediamine, octamethylenediamine and decamethylenediamine. The diamine used to form the sulfonic acid salt may be the same as or different from that used to form the polyamide salt. The same or different diamines can thus be present when forming the polymers according to the invention.
De her beskrevne modifiserte syntetiske lineære polyamider fremstilles ved i faget velkjente metoder som anvendes alminnelig ved fabrikasjon av enkle polyamider. Re-aktantene opphetes altså ved temperaturer fra 180 til 300°C, fortrinnsvis fra 200 til 295°C, inntil produktet har en tilstrekkelig høy molekylvekt til å fremvise fiberdannende egenskaper. Denne betingelse nåes når polyamidet har en grenseviskositet på minst 0,4, overensstemmende med den forannevnte definisjon på grenseviskositet. The modified synthetic linear polyamides described here are produced by methods well known in the art which are generally used in the manufacture of simple polyamides. The reactants are therefore heated at temperatures from 180 to 300°C, preferably from 200 to 295°C, until the product has a sufficiently high molecular weight to exhibit fibre-forming properties. This condition is reached when the polyamide has an intrinsic viscosity of at least 0.4, consistent with the aforementioned definition of intrinsic viscosity.
Reaksjonen kan foregå ved et trykk over, The reaction can take place by pressing above,
lik, eller under atmosfæretrykk. Det er ofte equal to, or below, atmospheric pressure. It is often
ønskelig, spesielt under reaksjonens siste trinn, å anvende betingelser som f. eks. redusert trykk som vil bidra til å fjerne bi-produktene ved reaksjonen. De foran opp-regnede sulfonsyrer eller diaminene av desirable, especially during the last step of the reaction, to apply conditions such as reduced pressure which will help to remove the by-products of the reaction. The sulfonic acids or diamines listed above of
disse kan settes polymeriserings-autoklaven sammen med de polyamiddannende reaktanter eller hver for seg, før eller etter at polymeriseringsreaksjonen er begynt. De konvensjonelle polyamid-dannende reaktanter innføres normalt som et på forhånd dannet salt, men kan også foreligge i form av uomsatt diamin og dicarboxylsyre når de settes til autoklaven. these can be put in the polymerization autoclave together with the polyamide-forming reactants or separately, before or after the polymerization reaction has begun. The conventional polyamide-forming reactants are normally introduced as a pre-formed salt, but can also be present in the form of unreacted diamine and dicarboxylic acid when added to the autoclave.
For å illustrere oppfinnelsen, henvises til de etterfølgende eksempler. Deler er vektsdeler, dersom intet annet er nevnt. To illustrate the invention, reference is made to the following examples. Parts are parts by weight, if nothing else is mentioned.
Eksempel 1. Example 1.
Dette eksempel skal illustrere fremstilling av et konvensjonelt fiberdannende polyamid og skal tjene som en standard sammenligning med de modifiserte polyamider ifølge nærværende oppfinnelse. This example shall illustrate the production of a conventional fiber-forming polyamide and shall serve as a standard comparison with the modified polyamides according to the present invention.
En blanding av 48 kg 50 pst's vandig oppløsning av hexamethylendiammonium-adipat og 300 g av en vandig oppløsning inneholdende 25 pst. eddiksyre som en vis-kositets-stabilisator ble påfyllt en autoklav av rustfritt stål. Denne var på forhånd blitt befridd for luft ved hjelp av damp. Trykket og temperaturen ble langsomt øket til 17,8 kg/cms og 220°C. Tilstrekkelig meget titandioxyd i vandig suspensjon til å produsere et halv-glansgarn (0,3 pst. titandioxyd beregnet på den garnvekt som tilslutt var fremstillet) ble satt til før dette punkt idet temperaturen nådde 210°C. Vann ble deretter fjernet som kondensat. Trykket ble holdt konstant, inntil en temperatur på 243°C var oppnådd. På dette punkt begynte trykkreduksjons-cyklusen. Trykket falt til atmosfæretrykket i løpet av 90 minutter. Etter en 30 minutters cyklus ble det ferdige polymerisat støpt som et sammenhengende bånd, avkjølet og derpå skåret opp til grove skivelignende partikler. De oppnådde polymerisatskiver ble nu spunnet til garn på konvensjonelt smeltespinningsutstyr, og garnet ble strukket på en strekktvinner. Det endelige denier av 13-filament-garnet var 40. Forlengelse ved brudd var 27 pst. A mixture of 48 kg of a 50% aqueous solution of hexamethylenediammonium adipate and 300g of an aqueous solution containing 25% acetic acid as a viscosity stabilizer was charged to a stainless steel autoclave. This had previously been freed of air using steam. The pressure and temperature were slowly increased to 17.8 kg/cms and 220°C. Sufficient titanium dioxide in aqueous suspension to produce a semi-gloss yarn (0.3 percent titanium dioxide calculated on the weight of yarn finally produced) was added before this point as the temperature reached 210°C. Water was then removed as condensate. The pressure was kept constant until a temperature of 243°C was reached. At this point the pressure reduction cycle began. The pressure dropped to atmospheric pressure within 90 minutes. After a 30 minute cycle, the finished polymer was cast as a continuous band, cooled and then cut into coarse disc-like particles. The resulting polymer discs were now spun into yarn on conventional melt spinning equipment, and the yarn was stretched on a stretch winder. The final denier of the 13-filament yarn was 40. Elongation at break was 27 percent.
Eksempel 2. Example 2.
En blanding av 48 kg 50 pst.'s vannholdig oppløsning av hexamethylendiammonium-adipat fremstilt av ekvimolekylære mengder av adipinsyre og hexamethylendiamin og 400 g av en vannholdig oppløsning inneholdende 25 pst. eddiksyre som en viskosi-tets-stabilisator ble påfyllt en autoklav av rustfritt stål. Denne var på forhånd blitt befridd for luft ved hjelp av damp. Trykket og temperaturen ble langsomt øket, og da temperaturen nådde 170°C, ble der tilsatt 266 g p-toluensulfonsyre. Da temperaturen nådde 210°C, ble der tilsatt tilstrekkelig meget titandioxyd i vandig suspensjon for å produsere et halvskinnende garn (0,3 pst. titandioxyd beregnet på vekten av det endelige garn). Vann ble derpå fjernet som kondensat. Trykket ble holdt konstant ved 17,8 kg/cm2, inntil en temperatur på 243°C var nådd. På dette punkt begynte trykk-reduksjonscyklusen. Trykket ble minsket til atmosfæretrykket under en 90 minutters periode. Etter en 30 minutters cyklus ble det ferdige polymerisat støpt som et sammenhengende bånd og skåret opp til grove skivelignende partikler. De oppnådde polymerisatskiver ble spunnet til garn som før, og garnet ble strukket til en 27 pst.'s forlengelse. Det endelige denier av 13-filamentgarnet var 40. A mixture of 48 kg of a 50% aqueous solution of hexamethylenediammonium adipate prepared from equimolecular amounts of adipic acid and hexamethylenediamine and 400g of an aqueous solution containing 25% acetic acid as a viscosity stabilizer was charged into a stainless steel autoclave. . This had previously been freed of air using steam. The pressure and temperature were slowly increased, and when the temperature reached 170°C, 266 g of p-toluenesulfonic acid were added. When the temperature reached 210°C, sufficient titanium dioxide was added in aqueous suspension to produce a semi-shiny yarn (0.3 percent titanium dioxide calculated on the weight of the final yarn). Water was then removed as condensate. The pressure was kept constant at 17.8 kg/cm 2 until a temperature of 243°C was reached. At this point the pressure reduction cycle began. The pressure was reduced to atmospheric pressure over a 90 minute period. After a 30 minute cycle, the finished polymer was cast as a continuous band and cut up into coarse disc-like particles. The resulting polymer discs were spun into yarn as before, and the yarn was stretched to a 27% elongation. The final denier of the 13 filament yarn was 40.
Eksempel 3. Example 3.
En blanding av 48 kg 50 pst.'s vannholdig oppløsning av hexamethylendiammoni-umadipat fremstilt av ekvimolære mengder adipinsyre og hexamethylendiamin og 400 g av en vandig oppløsning inneholdende 25 pst. eddiksyre som en viskositetsstabilisator ble påfyllt en autoklav av rustfritt stål. Denne var på forhånd blitt befridd for luft ved hjelp av damp. Trykket og temperaturen ble langsomt øket, og da temperaturen nådde 170°C, ble der tilsatt 530 g p-toluensulfonsyre. Da temperaturen nådde 210°C, ble der tilsatt tilstrekkelig meget titandioxyd i vandig suspensjon for å produsere et halvskinnende garn (0,3 pst. titandioxyd på garnets vekt som tilslutt ble oppnådd). Vann ble derpå fjernet som kondensat. Trykket ble holdt konstant ved 17,8 kg/cm2, inntil en temperatur på 243 °C var nådd. På dette punkt begynte trykk-reduksjonscyklusen. Trykket ble minsket til atmosfæretrykket under en 90 minutters periode. Etter en 30 minutters cyklus ble det ferdige polymerisat støpt som et sammenhengende bånd og skåret opp til grove skivelignende partikler. Polymerisat-skivene ble spunnet og strukket til 27 pst. forlengelse. Den endelige denier av 13-filament-garnet var 40. A mixture of 48 kg of a 50% aqueous solution of hexamethylenediammonium umadipate prepared from equimolar amounts of adipic acid and hexamethylenediamine and 400g of an aqueous solution containing 25% acetic acid as a viscosity stabilizer was charged to a stainless steel autoclave. This had previously been freed of air using steam. The pressure and temperature were slowly increased, and when the temperature reached 170°C, 530 g of p-toluenesulfonic acid were added. When the temperature reached 210°C, a sufficient amount of titanium dioxide was added in aqueous suspension to produce a semi-shiny yarn (0.3 percent titanium dioxide on the weight of the yarn that was finally obtained). Water was then removed as condensate. The pressure was kept constant at 17.8 kg/cm 2 until a temperature of 243 °C was reached. At this point the pressure reduction cycle began. The pressure was reduced to atmospheric pressure over a 90 minute period. After a 30 minute cycle, the finished polymer was cast as a continuous band and cut up into coarse disc-like particles. The polymer discs were spun and stretched to 27 percent elongation. The final denier of the 13-filament yarn was 40.
Eksempel 4. Example 4.
En blanding av 48 kg 50 pst.'s vannholdig oppløsning av hexamethylendiam-moniumadipat og 300 g av en vandig opp-løsning inneholdende 25 pst. eddiksyre som en viskositetsstabilisator ble påfyllt en autoklav av rustfritt stål. Denne var på forhånd blitt befridd for luft ved hjelp av damp. Trykket og temperaturen ble langsomt øket, og da temperaturen nådde 170° C, ble der tilsatt 1,05 mol-pst. av ethansulfonsyre, basert på hexamethylendiammo-niumadipatet. Da temperaturen nådde 210° C, ble tilstrekkelig meget titandioxyd i vandig dispersjon tilsatt for å produsere et halvglansgarn (0,3 pst. titandioxyd basert på det tilslutt oppnådde garns vekt). Vann ble derpå fjernet som kondensat. Trykket ble holdt konstant ved 17,8 kg/cm?, inntil en temperatur på 243°C var oppnådd. På dette punkt begynte trykkreduksjonscyklu-sen. Trykket ble redusert til atmosfæretrykk over en 90 minutters periode. Etter en cyklus av 30 minutters varighet, ble slutt-polymerisatet støpt til et sammenhengende bånd som deretter ble skåret opp i grove skivelignende partikler. Disse ble spunnet til garn på standard smeltespinningsutstyr, og garnet ble strukket til 27 pst.'s forlengelse. Den endelige denier av 13-filament-garnet var 40. A mixture of 48 kg of a 50% aqueous solution of hexamethylenediamonium adipate and 300g of an aqueous solution containing 25% acetic acid as a viscosity stabilizer was charged to a stainless steel autoclave. This had previously been freed of air using steam. The pressure and temperature were slowly increased, and when the temperature reached 170° C, 1.05 mole percent was added. of ethanesulfonic acid, based on the hexamethylene diammonium adipate. When the temperature reached 210° C, a sufficient amount of titanium dioxide in aqueous dispersion was added to produce a semi-gloss yarn (0.3 percent titanium dioxide based on the weight of the finally obtained yarn). Water was then removed as condensate. The pressure was kept constant at 17.8 kg/cm 2 until a temperature of 243°C was reached. At this point the pressure reduction cycle began. The pressure was reduced to atmospheric pressure over a 90 minute period. After a cycle of 30 minutes duration, the final polymer was cast into a continuous ribbon which was then cut into coarse disc-like particles. These were spun into yarn on standard melt spinning equipment, and the yarn was stretched to 27 percent elongation. The final denier of the 13-filament yarn was 40.
For å demonstrere den praktiske bruk-barhet av de modifiserte polyamider ifølge oppfinnelsen, ble der utført sammenlignen-de prøver på produktene i henhold til de foregående eksempler for å bestemme den relative mottagelighet for de nevnte farvestoffer. Tøyprøver oppnådd av garn som nevnt i hvert av de foregående eksempler ble farvet med sammenlignbare konsentra-sjoner av det kommersielle f arvestoff In order to demonstrate the practical usability of the modified polyamides according to the invention, comparative tests were carried out on the products according to the previous examples to determine the relative receptivity to the mentioned dyes. Fabric samples obtained from yarn as mentioned in each of the preceding examples were dyed with comparable concentrations of the commercial dyestuff
«Scarlet 4RA» (C. J. Acid Red 18) svarende til formelen: "Scarlet 4RA" (C. J. Acid Red 18) corresponding to the formula:
■f. ■ f.
Farvningen ble utført i et bad, hvori sentrasjon, dvs. forskjellen mellom den forholdet mellom lut og fiber var 40:1. Ba- opprinnelige farvekonsentrasjon og kon-dets temperatur ble holdt på 100°C, og far- sentrasjonen, etterat likevektsbetingelsene vetiden var to timer lang. Farveabsorp- var nådd. De oppnådde resultater var føl-sjonsgraden ble bestemt ved å måle spek- gende: The dyeing was carried out in a bath, in which concentration, i.e. the difference between the ratio between lye and fiber was 40:1. Ba- initial dye concentration and condenser temperature were kept at 100°C, and the father concentration, after equilibrium conditions, the waiting time was two hours long. Color absorption was reached. The results obtained were the degree of sensation was determined by measuring the following:
trofotometrisk forandringene i badets kon- trophotometrically the changes in the bath's con-
Av denne tabell fremgår at tøyer fremstillet av polymerisater oppnådd overen-stemmende med oppfinnelsen, kan absorbere vesentlig mere surt farvestoff enn tøyer som er fremstillet av konvensjonelle polyamider. From this table it appears that fabrics made from polymers obtained in accordance with the invention can absorb significantly more acid dyes than fabrics made from conventional polyamides.
Farvningsresultater i likhet med dem Staining results like them
som er vist i tabellen oppnåes når sulfonsyren i hvert av eksemplene erstattes med en ekvivalent molar mengde av det tilsvarende diaminsalt. Således kan f. eks. hexa- which is shown in the table is obtained when the sulphonic acid in each of the examples is replaced by an equivalent molar amount of the corresponding diamine salt. Thus, e.g. hexa-
methylendiaminsaltet av p-toluensulfonsyre med like gode farveabsorpsjonsresul-tater anvendes i stedet for p-toluensulfonsyre i eksempel 2. The methylenediamine salt of p-toluenesulfonic acid with equally good color absorption results is used instead of p-toluenesulfonic acid in example 2.
For ytterligere å illustrere prinsippene og praksis ved nærværende oppfinnelse, ble der foretatt målinger av farvegraden for sammenligning med eksempel 1 (kont-roll) og eksempel 3. Det anvendte farvestoff var det ovennevnte «Scarlet 4RA» (C. J. Acid Red 18) som ble anvendt i kon-sentrasj onen 4,0 pst. på tøyets vekt i et farvestoffbad, hvori forholdet mellom lut og fiber var som 65:1. Farvestoffbadet ble holdt på en temperatur av 60°C. Farvingen ble foretatt inntil den halve farvingstid var nådd, dvs. den tid som var nødvendig for å få fiberen til å absorbere farvestoff tilsvarende halvdelen av sin kapasitet. Spesielle farvehastighetskonstanter ble deretter bestemt overensstemmende med det følgende uttrykk: To further illustrate the principles and practice of the present invention, measurements were made of the degree of color for comparison with example 1 (control) and example 3. The dye used was the above-mentioned "Scarlet 4RA" (C.J. Acid Red 18) which was used in a concentration of 4.0 per cent on the weight of the cloth in a dye bath, in which the ratio between lye and fiber was 65:1. The dye bath was kept at a temperature of 60°C. The dyeing was carried out until half the dyeing time had been reached, i.e. the time required for the fiber to absorb dye corresponding to half of its capacity. Specific color speed constants were then determined according to the following expression:
hvor K, =spesifikk farvehastighetskons-tant C„o=farveabsorpsjon ved likevekt t l/2=halvfarvningstiden, dvs. tiden i minutter for fibrenes ab-sorpsjon av halvdelen av deres farvestoffkapasitet d=filamentdenier. where K, =specific dye rate constant C„o=dye absorption at equilibrium t l/2=half-dyeing time, i.e. the time in minutes for the fibers to absorb half of their dye capacity d=filament denier.
Følgende resultater ble oppnådd ved de foran beskrevne bestemmelser: The following results were obtained by the provisions described above:
Ved å sammenligne de spesifikke farvehastighetskonstanter (K,) i denne tabell, vil det sees at farvehastigheten for det modifiserte polyamid (eksempel 3) er mer enn den dobbelte av hastigheten for kont-rollprøven (eksempel 1). By comparing the specific color fastness constants (K,) in this table, it will be seen that the color fastness of the modified polyamide (Example 3) is more than double the speed of the control sample (Example 1).
De foregående eksempler og de nevnte prøveresultater i forbindelse dermed viser klart at de modifiserte polyamider ifølge denne oppfinnelse representerer fremtre-dende forbedringer sammenlignet med umodifiserte polyamider, hva deres mottagelighet for sure farvestoffer angår. Skjønt oppfinnelsen ikke ønsker å være bundet til noen teori, hva selve mekanismen angår, postuleres det at polyamidmodifi-kasjonen ifølge oppfinnelsen innebærer reaksjon mellom det modifiserte middel og de diaminer som anvendes ved dannelse av polyamidet, slik at man unngår tap av diamin fra den polyamid-dannende reak-sjonssone. Da de diaminer som anvendes for dannelse av syntetiske lineære polyamider er forholdsvis flyktige, oppstår der ifølge erfaringer normalt tap under den polyamid-dannende reaksjon. Det resulte-rende polymerisat har følgelig et mindre antall amin-endegrupper enn hva der el-lers ville være tilgjengelig for å skaffe fes-tepunkt for sure farvestoffer. Disse tap av diamin unngåes ved at man binder dette ved hjelp av et modifiserende middel med hvilket det reagerer. The previous examples and the test results mentioned in connection with this clearly show that the modified polyamides according to this invention represent prominent improvements compared to unmodified polyamides, as far as their receptivity to acid dyes is concerned. Although the invention does not wish to be bound by any theory, as far as the mechanism itself is concerned, it is postulated that the polyamide modification according to the invention involves a reaction between the modified agent and the diamines used in the formation of the polyamide, so that loss of diamine from the polyamide is avoided -forming reaction zone. As the diamines used for the formation of synthetic linear polyamides are relatively volatile, according to experience, losses normally occur during the polyamide-forming reaction. The resulting polymer consequently has a smaller number of amine end groups than would otherwise be available to provide attachment points for acidic dyes. These losses of diamine are avoided by binding this with the help of a modifying agent with which it reacts.
De modifiserte polyamider ifølge denne oppfinnelse er av største interesse til bruk ved garn og tøy. Men de er like brukbare i andre sluttprodukter hvor en øket mottagelighet for farvestoffer kan være ønskelig, f. eks. ved bust, film og lignende. The modified polyamides according to this invention are of greatest interest for use in yarn and cloth. But they are equally usable in other end products where an increased receptivity to dyes may be desirable, e.g. by brush, film and the like.
Ved fremstilling av polyamidene ifølge denne oppfinnelse kan der tilsettes andre modifiserende midler, f. eks. matterings-midler, antioxydanter, myknere, osv. When producing the polyamides according to this invention, other modifying agents can be added, e.g. matting agents, antioxidants, plasticizers, etc.
Claims (2)
Applications Claiming Priority (1)
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US45509974A | 1974-03-27 | 1974-03-27 |
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JP (1) | JPS5822478B2 (en) |
BE (1) | BE826873A (en) |
CA (1) | CA1055528A (en) |
CH (1) | CH612932A5 (en) |
DE (1) | DE2513806A1 (en) |
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FI (1) | FI62065C (en) |
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SE (1) | SE424548B (en) |
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US4117128A (en) | 1976-08-03 | 1978-09-26 | Smithkline Corporation | Sulfonyl benzofurans and benzothiophenes having coronary vasodilator activity |
JP2925035B2 (en) * | 1993-12-07 | 1999-07-26 | エス・ウント・エル・マシイネンバウ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Method and apparatus for baking a cake |
US6358515B2 (en) | 1997-01-30 | 2002-03-19 | Senju Pharmaceutical Co., Ltd. | Hydroquinone derivatives |
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1975
- 1975-03-11 CA CA221,803A patent/CA1055528A/en not_active Expired
- 1975-03-12 YU YU00591/75A patent/YU59175A/en unknown
- 1975-03-19 BE BE154495A patent/BE826873A/en unknown
- 1975-03-20 LU LU72100A patent/LU72100A1/xx unknown
- 1975-03-20 JP JP50033124A patent/JPS5822478B2/en not_active Expired
- 1975-03-24 FR FR7509047A patent/FR2265358B1/fr not_active Expired
- 1975-03-24 FI FI750875A patent/FI62065C/en not_active IP Right Cessation
- 1975-03-24 NL NL7503489A patent/NL7503489A/en not_active Application Discontinuation
- 1975-03-24 ZA ZA00751853A patent/ZA751853B/en unknown
- 1975-03-24 DK DK123875A patent/DK144246C/en active
- 1975-03-24 NO NO750993A patent/NO140856C/en unknown
- 1975-03-26 IE IE670/75A patent/IE40887B1/en unknown
- 1975-03-26 GB GB1265275A patent/GB1451180A/en not_active Expired
- 1975-03-26 SE SE7503582A patent/SE424548B/en unknown
- 1975-03-27 CH CH399675A patent/CH612932A5/en not_active IP Right Cessation
- 1975-03-27 DE DE19752513806 patent/DE2513806A1/en not_active Ceased
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1978
- 1978-08-31 FR FR7825229A patent/FR2391725A1/en active Granted
-
1982
- 1982-06-03 YU YU01171/82A patent/YU117182A/en unknown
Also Published As
Publication number | Publication date |
---|---|
FR2265358A1 (en) | 1975-10-24 |
CA1055528A (en) | 1979-05-29 |
NO750993L (en) | 1975-09-30 |
DK123875A (en) | 1975-09-28 |
YU59175A (en) | 1982-10-31 |
AU7839175A (en) | 1976-08-26 |
LU72100A1 (en) | 1976-02-04 |
NL7503489A (en) | 1975-09-30 |
GB1451180A (en) | 1976-09-29 |
ZA751853B (en) | 1976-02-25 |
DK144246B (en) | 1982-01-25 |
IE40887B1 (en) | 1979-09-12 |
FR2265358B1 (en) | 1980-02-08 |
NO140856C (en) | 1979-11-28 |
SE7503582L (en) | 1975-09-29 |
FR2391725B1 (en) | 1981-07-17 |
YU117182A (en) | 1982-10-31 |
CH612932A5 (en) | 1979-08-31 |
JPS50130736A (en) | 1975-10-16 |
DK144246C (en) | 1982-06-28 |
FR2391725A1 (en) | 1978-12-22 |
DE2513806A1 (en) | 1975-10-09 |
SE424548B (en) | 1982-07-26 |
FI62065C (en) | 1982-11-10 |
IE40887L (en) | 1975-09-27 |
BE826873A (en) | 1975-09-19 |
FI62065B (en) | 1982-07-30 |
FI750875A (en) | 1975-09-28 |
JPS5822478B2 (en) | 1983-05-09 |
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