DE1173207B - Manufacture of threads, fibers or films - Google Patents
Manufacture of threads, fibers or filmsInfo
- Publication number
- DE1173207B DE1173207B DEF20329A DEF0020329A DE1173207B DE 1173207 B DE1173207 B DE 1173207B DE F20329 A DEF20329 A DE F20329A DE F0020329 A DEF0020329 A DE F0020329A DE 1173207 B DE1173207 B DE 1173207B
- Authority
- DE
- Germany
- Prior art keywords
- fibers
- films
- separated
- threads
- polyesters
- 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.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920000728 polyester Polymers 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 14
- -1 halides Dicarboxylic acids Chemical class 0.000 claims description 13
- 150000002989 phenols Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000008018 melting Effects 0.000 description 9
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- IQNTUYCIRRCRDY-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=C(C(Cl)=O)C=C1Cl IQNTUYCIRRCRDY-UHFFFAOYSA-N 0.000 description 1
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- SLABEOONBHLKSD-UHFFFAOYSA-N O=S1(=O)C(C=C2)=CC=C2OOC2=CC=C1C=C2 Chemical compound O=S1(=O)C(C=C2)=CC=C2OOC2=CC=C1C=C2 SLABEOONBHLKSD-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YAZXITQPRUBWGP-UHFFFAOYSA-N benzene-1,3-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=CC(C(Br)=O)=C1 YAZXITQPRUBWGP-UHFFFAOYSA-N 0.000 description 1
- QAOMIRAFWBTGIR-UHFFFAOYSA-N benzene-1,4-dicarbonyl fluoride Chemical compound FC(=O)C1=CC=C(C(F)=O)C=C1 QAOMIRAFWBTGIR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Artificial Filaments (AREA)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Internat. KL: DOIf Boarding school KL: DOIf
Deutsche KL: 29 b - 3/60 German KL: 29 b - 3/60
Nummer: 1 173 207Number: 1 173 207
Aktenzeichen: F 20329IV c / 29 bFile number: F 20329IV c / 29 b
Anmeldetag: 18. Mai 1956Filing date: May 18, 1956
Auslegetag: 2. Juli 1964Opening day: July 2nd, 1964
Hochschmelzende lineare Polyester von Dicarbonsäuren, die zur Verarbeitung zu Fasern oder Folien bestimmt sind, werden bisher praktisch nur aus aromatischen Dicarbonsäuren oder deren funktioneilen Derivaten, insbesondere Estern und niederen aliphatischen Glykolen, vor allem Äthylenglykol, hergestellt. Es sind aber auch schon Polyester von aliphatischen Dicarbonsäuren mit zweiwertigen Phenolen synthetisiert und für die Verarbeitung auf Fasern in Vorschlag gebracht worden. Die Eigenschaften derartiger Stoffe sind indessen so wenig befriedigend, daß diese Versuche ohne Bedeutung geblieben sind. Noch die besten Resultate erhielt man durch Umestern von Diacylaten aromatischer Dioxyverbindungen mit einbasischen, flüchtigen Säuren, wie Essigsäure, mit freien aliphatischen Dicarbonsäuren in Gegenwart von sauren Umesterungskatalysatoren. Die nach diesem Verfahren hergestellten Produkte sind aber in der Regel nicht farblos und besitzen auch nicht den Polykondensationsgrad der in der Technik für Faserherstellung verwendeten linearen Polyester. Auch bei der Umsetzung von zweiwertigen Phenolen mit aliphatischen Dicarbonsäurechloriden in Gegenwart von Alkalihydroxyd sind nach Angaben der Literatur keine für die Verspinnung wirklich geeignete Produkte erhalten worden. Zudem sind auch diese Polykondensate mehr oder weniger stark verfärbt. Schließlich hat man noch durch Erhitzen von Chloriden zweibasischer aliphatischer Dicarbonsäuren mit Dioxybenzolen, wie Hydrochinon, in indifferenten Mitteln Polykondensate mit Schmelzpunkten von etwa 2300C erhalten, die aus der Schmelze zu Fäden versponnen werden konnten. Dabei hat sich aber gezeigt, daß Polymere dieser Art thermisch nicht stabil sind und daß sie aus diesem Grund zur Herstellung von Fasern nicht in Betracht kommen.High-melting linear polyesters of dicarboxylic acids, which are intended for processing into fibers or films, have hitherto been produced practically only from aromatic dicarboxylic acids or their functional derivatives, in particular esters and lower aliphatic glycols, especially ethylene glycol. However, polyesters of aliphatic dicarboxylic acids with dihydric phenols have also been synthesized and proposed for processing on fibers. The properties of such substances are, however, so unsatisfactory that these attempts are of no importance. The best results were obtained by transesterifying diacylates of aromatic dioxy compounds with monobasic, volatile acids, such as acetic acid, with free aliphatic dicarboxylic acids in the presence of acidic transesterification catalysts. However, the products manufactured by this process are generally not colorless and also do not have the degree of polycondensation of the linear polyesters used in fiber manufacturing technology. Even when dihydric phenols are reacted with aliphatic dicarboxylic acid chlorides in the presence of alkali hydroxide, no products really suitable for spinning have been obtained, according to the literature. In addition, these polycondensates are also discolored to a greater or lesser extent. Finally, one has yet by heating chlorides of dibasic aliphatic dicarboxylic acids having Dioxybenzolen, such as hydroquinone, obtained in indifferent agents polycondensates having melting points of about 230 0 C, which could be spun from the melt into filaments. It has been shown, however, that polymers of this type are not thermally stable and that, for this reason, they cannot be used for the production of fibers.
Aus der USA--Patentschrift 2035 578 war es bekannt, unter anderem aus freien zweiwertigen Phenolen, in denen die Hydroxylgruppen durch mindestens 3 Kohlenstoffatome getrennt sind, und Halogeniden aromatischer Dicarbonsäuren, in denen die Carbonylgruppen durch mindestens 3 Kohlenstoffatome getrennt sind, in Abwesenheit von Wasser Polyester herzustellen, die als Harze beim Erhitzen dieser Komponenten erhalten wurden. Verwendung fanden diese Harze allein oder in Mischung mit natürlichen oder künstlichen Harzen, Ölen oder Zellulosederivaten vor allem zur Herstellung von Anstrichen.It was known from the USA patent specification 2035 578, among other things from free divalent Phenols in which the hydroxyl groups are separated by at least 3 carbon atoms, and Halides of aromatic dicarboxylic acids in which the carbonyl groups are replaced by at least 3 carbon atoms are separated, in the absence of water, to produce polyesters that act as resins when heated of these components were obtained. These resins were used alone or in a mixture with natural or artificial resins, oils or cellulose derivatives, especially for the production of Painting.
Bei dieser Sachlage war es überraschend, daß hochschmelzende, in bekannter Weise hergestellte Herstellung von Fäden, Fasern oder FilmenGiven this situation, it was surprising that high-melting points produced in a known manner Manufacture of threads, fibers or films
Anmelder:Applicant:
Farbwerke Hoechst AktiengesellschaftFarbwerke Hoechst Aktiengesellschaft
vormals Meister Lucius & Brüning, Frankfurt/M.formerly Master Lucius & Brüning, Frankfurt / M.
Als Erfinder benannt:Named as inventor:
Dr. Paul Schlack,Dr. Paul Schlack,
Stetten (Filder) über Stuttgart-VaihingenStetten (Filder) via Stuttgart-Vaihingen
Polyester der im vorangegangenen Absatz bezeichneten Art, wenn sie eine relative Viskosität von wenigstens 1,4 aufweisen, zur Herstellung von Fäden, Fasern oder Filmen verwendet werden können.Polyester of the type described in the previous paragraph, if they have a relative viscosity of have at least 1.4, can be used for the production of threads, fibers or films.
Für das Verfahren der Erfindung kommen Polyester in Frage, zu deren an sich bekannten Herstellung beispielsweise folgende Dicarbonsäuredihalogenide verwendet wurden: Terephthalsäure-dichlorid, Terephthalsäure - difluorid, Isophthalsäuredichlorid, Isophthalsäure - dibromid, 5 - tert. - Butylisophthalsäure-dichlorid, Monochlorterephthalsäuredichlorid, 2,5-DichIorterephthalsäure-dichlorid, Diphenyläther-4,4'-dicarbonsäure-dichIorid, Diphenoxyäthan - 4,4' - dicarbonsäure - dichlorid, Diphenylmethan^^'-dicarbonsäure-dichlorid. For the process of the invention, polyesters are suitable for their production, which is known per se For example, the following dicarboxylic acid dihalides were used: terephthalic acid dichloride, Terephthalic acid - difluoride, isophthalic acid dichloride, Isophthalic acid - dibromide, 5 - tert. - butyl isophthalic acid dichloride, Monochloroterephthalic acid dichloride, 2,5-dichloroterephthalic acid dichloride, diphenyl ether-4,4'-dicarboxylic acid dichloride, Diphenoxyethane - 4,4 '- dicarboxylic acid - dichloride, Diphenylmethane ^^' - dicarboxylic acid dichloride.
Auch bei den zur Herstellung der erfindungsgemäß zur Bildung von Fäden, Fasern oder Filmen befähigten Polyestern verwendeten phenolischen Dioxyverbindungen sollen die Hydroxylgruppen durch mindestens 3 Kohlenstoffatome getrennt sein. Demnach kommen beispielsweise folgende zweiwertige Phenole in Betracht: Hydrochinon, Resorcin, 4,4' - Dioxydiphenybnethan, Methyl - di - [4 - oxyphenyl]-methan, Dknethyl-di-[4-oxyphenyl]-methan, MethyI-äthyl-di-[4-oxyphenyl]-methan, Diäthyl-di-[4 - oxyphenyl] - methan, 4,4' - Dioxy - diphenylsulfon, l,2-Bis-[4-oxyphenyl]-äthan, 4,4'-Dioxy-diphenoxyäthan, l,4-Bis-[4-oxy-phenoxy]-butan, 2,6-Dioxynaphthalin, 2,7 - Dioxy - naphthalin, 4,4' - Dioxy-1,10-di-p-oxyphenyldekan, 4,4'-DioxydiphenyI.Even with those for the production of the invention for the formation of threads, fibers or films Capable polyesters used phenolic dioxy compounds are said to contain the hydroxyl groups separated by at least 3 carbon atoms. Thus, for example, the following two-valued come Phenols in consideration: hydroquinone, resorcinol, 4,4 '- dioxydiphenybnethan, methyl - di - [4 - oxyphenyl] methane, Dknethyl-di- [4-oxyphenyl] -methane, methyl-ethyl-di- [4-oxyphenyl] -methane, diethyl-di- [4 - oxyphenyl] methane, 4,4 '- dioxy - diphenyl sulfone, 1,2-bis [4-oxyphenyl] ethane, 4,4'-dioxy-diphenoxyethane, 1,4-bis [4-oxy-phenoxy] butane, 2,6-dioxynaphthalene, 2,7 - Dioxy - naphthalene, 4,4 '- Dioxy-1,10-di-p-oxyphenyldecane, 4,4'-dioxydiphenyl.
Besonders bevorzugt sind für die Herstellung von Fäden, Fasern oder Filmen nach der Erfindung Polyester, die als Komponente zweikernige Phenole enthalten, in denen die Benzolkerne durch einen aliphatischen Rest getrennt sind, und von diesenAre particularly preferred for the production of threads, fibers or films according to the invention Polyesters that contain binuclear phenols as a component, in which the benzene nuclei are replaced by a aliphatic radical are separated, and from these
409 628/300409 628/300
wiederum die Dioxydiarylmethane, in denen der Methankohlenstoff durch wenigstens einen, vorzugsweise durch zwei aliphatische Reste oder durch eine Alkylenkette substituiert ist. Die Polyester aus diesen Dioxyverbindungen zeichnen sich aus durch ungewohnlich hohe thermische Beständigkeit, durch hellen Farbton und bei richtiger Wahl der Komponenten bzw. zweckmäßiger Einstellung des Schmelzpunktes in der Regel auch durch besonders gute Spinnbarkeit.turn the dioxydiarylmethanes, in which the Methane carbon by at least one, preferably by two aliphatic radicals or by one Alkylene chain is substituted. The polyesters from these dioxy compounds are characterized by unusual high thermal resistance, due to light color and with the right choice of components or appropriate setting of the melting point usually also by particularly good ones Spinnability.
Man wählt die Komponenten zweckmäßig so, daß die Schmelzpunkte der Polyester nicht über 33O°C, vorzugsweise nicht über 3000C, liegen. Bei Kombination mit einfachen Dioxybenzolen, z. B. Hydrochinon, erreicht man dies am besten dadurch, daß man zweikernige aromatische Dicarbonsäuredihalogenide benutzt, in denen die Kerne durch einen längeren aliphatischen Rest, der auch über Äthersauerstoff an diese Kerne gebunden sein kann, getrennt sind.The components is chosen appropriately so that the melting points of the polyester non-33O ° C, preferably not more than 300 0 C, are. When combined with simple dioxybenzenes, e.g. B. hydroquinone, this is best achieved by using binuclear aromatic dicarboxylic acid dihalides in which the nuclei are separated by a longer aliphatic radical which can also be bonded to these nuclei via ether oxygen.
Bei der hier nicht beanspruchten Herstellung hochschmelzender, für das Verspinnen zu Fasern geeigneter Polyester empfiehlt sich die Anwendung von Verdünnungsmitteln, die bei Reaktionstemperatur mindestens die Ausgangsstoffe zu lösen vermögen. Die Lösung braucht jedoch keine vollständige zu sein, wenn schon dieser Zustand bevorzugt wird.In the production of high-melting points, which is not claimed here, for spinning into fibers Suitable polyester is recommended to use diluents that are at the reaction temperature at least able to dissolve the starting materials. However, the solution does not need a complete one to be when this state is preferred.
Geeignete Lösungs- bzw. Verdünnungsmittel sind z. B. Kohlenwasserstoffe, wie Cyclohexan, Benzol, Toluol, Cumol, Tetrahydronaphthalin, a-Methylnaphthalin, Halogenkohlenwasserstoffe, wie Methylchloroform, Tetrachloräthylen, Monochlorbenzol, o-Dichlorbenzol, Trichlorbenzole, Monochlornaphthalin, Äther, wie Diphenyläther, Diphenyloxyd und Diphenylgemisch (azeotropisches Gemisch aus Diphenyl und Diphenyloxyd).Suitable solvents or diluents are, for. B. hydrocarbons, such as cyclohexane, benzene, Toluene, cumene, tetrahydronaphthalene, a-methylnaphthalene, Halogenated hydrocarbons such as methyl chloroform, tetrachlorethylene, monochlorobenzene, o-dichlorobenzene, trichlorobenzenes, monochloronaphthalene, Ethers, such as diphenyl ether, diphenyl oxide and diphenyl mixture (azeotropic mixture of Diphenyl and diphenyl oxide).
Wegen ihrer Indifferenz bei günstigem Lösevermögen sind aromatische Stoffe bevorzugt.Aromatic substances are preferred because of their indifference and good dissolving power.
Es ist erstaunlich, daß die Polykondensation aus aromatischen Dicarbonsäurehalogeniden, wie Terephthalsäurechlorid oder Isophthalsäurechlorid, mit zweikernigen Phenolen der oben bezeichneten Art bei richtiger Auswahl der Komponenten zur Vermeidung zu hoher Schmelzpunkte Produkte liefert, die nicht nur aus der Schmelze vorzüglich spinnbar sind, sondern sich trotz der Sperrigkeit des molekularen Baues in Form primärer Fäden teils schon bei Raumtemperatur, teils erst bei höherer Temperatur durch Recken zu wasserkochbeständigen, hochschmelzenden, mit Suspensionsfarbstoffen färbbaren Faserstoffen orientieren lassen. Auffällig ist, daß einzelne dieser Kombinationen trotz der Winkelstellung in wenigstens einer der Komponenten ungewöhnlich scharfe Schmelzpunkte besitzen, während z. B. das bekannte Polyäthylenisophthalat durch einen außerordentlich breiten Schmelzbereich gekennzeichnet ist, der die Verwendung dieses Polyesters zur Herstellung von Textilfasern praktisch ausschließt.It is astonishing that the polycondensation of aromatic dicarboxylic acid halides, such as terephthalic acid chloride or isophthalic acid chloride, with binuclear phenols of the type mentioned above Proper selection of components to avoid excessively high melting points delivers products that do not are only excellently spinnable from the melt, but despite the bulkiness of the molecular Build in the form of primary threads partly already at room temperature, partly only at a higher temperature Stretching to water-boiling-resistant, high-melting fibers that can be dyed with suspension dyes get oriented. It is noticeable that some of these combinations, despite the angular position in at least one of the components have unusually sharp melting points, while e.g. B. that known polyethylene isophthalate is characterized by an extraordinarily wide melting range, which practically excludes the use of this polyester for the production of textile fibers.
Bei Verwendung der bezeichneten Polyester zur Herstellung von Fasern, Fäden oder Filmen werden Produkte mit ausgezeichneten Eigenschaften erhalten. Sie besitzen nicht nur gute textile Eigenschaften, wie Festigkeit und Anfärbbarkeit, sondern darüber hinaus bei hohen Schmelzpunkten eine außerordentliche Beständigkeit gegen thermischen Abbau. Sie eignen sich daher in weit besserem Maße als solche aus Polyäthylenterephthalat zur Herstellung von Geweben oder Folien, die hohen Temperaturen ausgesetzt werden sollen, z. B. zur Wärmeisolierung verwendet werden sollen. Dadurch ergibt sich vor allem für die Filme ein weites Anwendungsgebiet, wobei noch hinzukommt, daß die Filme sich außerdem durch eine hervorragende Schmiegsamkeit auszeichnen.When using the designated polyester for the production of fibers, threads or films Obtain products with excellent properties. They not only have good textile properties, like strength and dyeability, but also at high melting points extraordinary resistance to thermal degradation. They are therefore far more suitable as such made of polyethylene terephthalate for the production of fabrics or films, the high temperatures are to be exposed, e.g. B. to be used for thermal insulation. This results in A wide field of application, especially for the films, with the fact that the films themselves also characterized by an excellent flexibility.
Aus nachfolgender Tabelle ist ersichtlich, wie der Schmelzpunkt durch die Wahl der Komponenten beeinflußt werden kann. Es ist zu bemerken, daß im Gegensatz zu den Polyamiden und den Polyestern der Terephthalsäure mit einfachen Glykolen der Schmelzpunkt dieser Arylester verhältnismäßig stark von der Kettenlänge abhängig ist.The table below shows how the melting point is determined by the choice of components can be influenced. It should be noted that in contrast to the polyamides and the polyesters of terephthalic acid with simple glycols, the melting point of these aryl esters is relatively high depends on the chain length.
Die Viskositätsmessungen beziehen sich auf 1 volumprozentige Lösungen in einer Mischung von Phenol und Tetrachloräthan im Gewichtsverhältnis 3 : 2. Meßtemperatur: 25°C.The viscosity measurements refer to 1 volume percent solutions in a mixture of Phenol and tetrachloroethane in a weight ratio of 3: 2. Measuring temperature: 25 ° C.
HI.
H
. ι , CH 3
. ι,
HH
CH3 I.
CH 3
Fortsetzungcontinuation
ιCH 3
ι
Zu einer Lösung von 11,42 g (V20 Mol) Dimethylbis-[4-oxyphenylj-methan in 150 ml wasserfreiem Benzol und 50 ml wasserfreiem Pyridin läßt man bei Siedetemperatur (85 0C) unter Durchleiten von reinem Stickstoff und unter kräftigem Rühren eine Lösung von 10,15 g (V20 Mol) Isophthalylchlorid in 80 ml wasserfreiem Benzol rasch zufließen. Schon nach kurzem Kochen beginnt die Abscheidung des Reaktionsproduktes. Nach 26stündigem Erhitzen wird das Reaktionsprodukt abgesaugt, dann der Rückstand erst mehrfach mit Alkohol, dann mit Wasser gewaschen und bei 1800C im Vakuum getrocknet. Die Ausbeute entspricht fast dem theoretischen Wert.To a solution of 11.42 g (V20 mol) of dimethylbis- [4-oxyphenylj-methanamine in 150 ml of anhydrous benzene and 50 ml of anhydrous pyridine is allowed at boiling temperature (85 0 C) while passing pure nitrogen and with vigorous stirring, a solution of 10.15 g (V20 mol) of isophthalyl chloride in 80 ml of anhydrous benzene flow rapidly. The reaction product begins to separate out after just a short boil. After heating for 26 hours, the reaction product is filtered off with suction, then the residue is washed several times with alcohol and then with water and dried at 180 ° C. in a vacuum. The yield almost corresponds to the theoretical value.
Der feinkörnige Polyester schmilzt zwischen 260 und 2700C zu einer farblosen, sehr gut verspinnbaren Schmelze. Die Fäden lassen sich bei Raumtemperatur oder auch in der Wärme, z. B. 1000C, durch Recken orientieren. Die relative Viskosität des Polyesters beträgt 1,64, entsprechend einem K-Wert von 48,8.The fine-grain polyester melts between 260 and 270 ° C. to form a colorless melt that can be spinned very well. The threads can be at room temperature or in the heat, for. B. 100 0 C, orientate by stretching. The relative viscosity of the polyester is 1.64, corresponding to a K value of 48.8.
5555
Zu einer Lösung von 6,765 g (1Ao Mol) 2,2-Bis-(4-oxyphenyl)-4-methyl-pentan in 200 ml wasserfreiem Toluol und 50 ml wasserfreiem Pyridin läßt man bei Siedetemperatur (1100C) unter Durchleiten von Stickstoff eine Lösung von 5,075 g (V-jo Mol) Terephthalylchlorid in 40 ml wasserfreiem Toluol rasch zufließen. Nach kurzer Zeit beginnt die Abscheidung des Reaktionsproduktes, jedoch wegen der guten Löslichkeit nur in geringem Maße. Die Aufarbeitung des Reaktionsproduktes erfolgt wie im Beispiel 1 angegeben. Das nach 15stündigem Kochen erhaltene Produkt schmilzt bei 270 bis 2800C und zeigt eine relative Viskosität von 1,458, entsprechend einem K-Wert von 41,5.To a solution of 6.765 g ( 1 Ao mol) of 2,2-bis- (4-oxyphenyl) -4-methyl-pentane in 200 ml of anhydrous toluene and 50 ml of anhydrous pyridine is allowed at boiling temperature (110 ° C.) while passing through A solution of 5.075 g (V-jo mol) of terephthalyl chloride in 40 ml of anhydrous toluene rapidly flow into nitrogen. The reaction product begins to separate out after a short time, but only to a small extent because of the good solubility. The reaction product is worked up as indicated in Example 1. The product obtained after 15 hours cooking melts at 270-280 0 C and shows a relative viscosity of 1.458, corresponding to a K value of 41.5.
Die aus der Schmelze gesponnenen Fäden lassen sich bei Raumtemperatur und in der Wärme recken.The threads spun from the melt can be stretched at room temperature and in the heat.
Das Polykondensat ist bei Raumtemperatur löslich in Methylenchlorid, Pyridin, Essigester, Phenol— Tetrachloräthan, ferner in heißem Benzol, Toluol, Xylol, Monochlorbenzol, o-Dichlorbenzol, Tetrahydronaphthalin, a-Methylnaphthalin, Dioxan, Dimethylformamid. The polycondensate is soluble in methylene chloride, pyridine, ethyl acetate, phenol at room temperature. Tetrachloroethane, also in hot benzene, toluene, xylene, monochlorobenzene, o-dichlorobenzene, tetrahydronaphthalene, α-methylnaphthalene, dioxane, dimethylformamide.
Wegen seiner guten Löslichkeit läßt sich dieser Polyester auch aus Lösungen auf z. B. Folien oder Überzüge verformen.Because of its good solubility, this polyester can also be prepared from solutions on z. B. foils or Deform coatings.
Claims (2)
Deutsche Patentschrift Nr. 818 117;
französische Patentschrift Nr. 975 729;
USA.-Patentschrift Nr. 2 035 578.Considered publications:
German Patent No. 818 117;
French Patent No. 975 729;
U.S. Patent No. 2,035,578.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB863704D GB863704A (en) | 1956-05-18 | ||
| DEF20329A DE1173207B (en) | 1956-05-18 | 1956-05-18 | Manufacture of threads, fibers or films |
| FR1175362D FR1175362A (en) | 1956-05-18 | 1957-05-17 | New polyesters and their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20329A DE1173207B (en) | 1956-05-18 | 1956-05-18 | Manufacture of threads, fibers or films |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1173207B true DE1173207B (en) | 1964-07-02 |
Family
ID=7089634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF20329A Pending DE1173207B (en) | 1956-05-18 | 1956-05-18 | Manufacture of threads, fibers or films |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE1173207B (en) |
| FR (1) | FR1175362A (en) |
| GB (1) | GB863704A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3194794A (en) * | 1960-01-27 | 1965-07-13 | Eastman Kodak Co | Process of preparing polymers of nuclearly polychlorinated aromatic dicarboxylic acids and diamines having at least 4 carbons |
| US3160603A (en) * | 1960-06-01 | 1964-12-08 | Gen Electric | Wholly aromatic poly-p-phenylene chloroisophthalates |
| NL129038C (en) * | 1960-06-01 | 1970-01-15 | Gen Electric | Method for preparing linear polyesters |
| US3160604A (en) * | 1961-06-01 | 1964-12-08 | Mbltino fo | |
| US3234167A (en) * | 1962-01-09 | 1966-02-08 | Du Pont | Light-stable aromatic polyesters |
| US3251804A (en) * | 1962-02-09 | 1966-05-17 | Du Pont | Poly(phenylene/4, 4'-diphenyleneisopropylidene hexahydroterephthalate) |
| US3256242A (en) * | 1962-11-14 | 1966-06-14 | Du Pont | Aromatic chloroisophthalate polyesters |
| US3309334A (en) * | 1963-07-12 | 1967-03-14 | Gen Electric | Polymeric copolyesters of phthalic acids, a bis-(hydroxyphenyl)alkane and a diphenolic acid |
| US3398120A (en) * | 1963-07-16 | 1968-08-20 | Hooker Chemical Corp | Polyesters of diacid halide, alkyl bisphenol and glycol |
| JPS5027061B1 (en) * | 1971-03-08 | 1975-09-04 | ||
| SE416814B (en) * | 1974-05-10 | 1981-02-09 | Du Pont | NEW SYNTHETIC POLYESTERS AND SETS FOR THEIR PREPARATION |
| DE3502378A1 (en) * | 1985-01-25 | 1986-07-31 | Bayer Ag, 5090 Leverkusen | THERMOTROPE AROMATIC POLYESTER WITH HIGH THERMAL STABILITY, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES, FILAMENTS, FIBERS AND FILMS |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2035578A (en) * | 1933-04-01 | 1936-03-31 | Du Pont | Synthetic resin |
| FR975729A (en) * | 1947-12-01 | 1951-03-08 | Courtaulds Ltd | Polymer esters and their preparation process |
| DE818117C (en) * | 1945-07-20 | 1951-08-30 | Imperial Chemical Industries Limited, London | Process for the preparation of high polymer linear esters |
-
0
- GB GB863704D patent/GB863704A/en not_active Expired
-
1956
- 1956-05-18 DE DEF20329A patent/DE1173207B/en active Pending
-
1957
- 1957-05-17 FR FR1175362D patent/FR1175362A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2035578A (en) * | 1933-04-01 | 1936-03-31 | Du Pont | Synthetic resin |
| DE818117C (en) * | 1945-07-20 | 1951-08-30 | Imperial Chemical Industries Limited, London | Process for the preparation of high polymer linear esters |
| FR975729A (en) * | 1947-12-01 | 1951-03-08 | Courtaulds Ltd | Polymer esters and their preparation process |
Also Published As
| Publication number | Publication date |
|---|---|
| GB863704A (en) | 1900-01-01 |
| FR1175362A (en) | 1959-03-24 |
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