CS242275B1 - Mixture of isotactic polypropylene suitable for dyeing foils and fibres production - Google Patents
Mixture of isotactic polypropylene suitable for dyeing foils and fibres production Download PDFInfo
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- CS242275B1 CS242275B1 CS846063A CS606384A CS242275B1 CS 242275 B1 CS242275 B1 CS 242275B1 CS 846063 A CS846063 A CS 846063A CS 606384 A CS606384 A CS 606384A CS 242275 B1 CS242275 B1 CS 242275B1
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- isotactic polypropylene
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- -1 polypropylene Polymers 0.000 title claims description 30
- 239000004743 Polypropylene Substances 0.000 title claims description 22
- 229920001155 polypropylene Polymers 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000004043 dyeing Methods 0.000 title description 5
- 239000011888 foil Substances 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 15
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 229920006163 vinyl copolymer Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005936 piperidyl group Chemical group 0.000 claims 1
- 238000005809 transesterification reaction Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 2
- 229960004025 sodium salicylate Drugs 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- WPARMABOLAOINO-UHFFFAOYSA-N 1,2,2,6,6-Pentamethyl-4-piperidinyl acrylate Chemical compound CN1C(C)(C)CC(OC(=O)C=C)CC1(C)C WPARMABOLAOINO-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- GOLSFPMYASLXJC-UHFFFAOYSA-N 2-(dimethylamino)ethyl acetate Chemical compound CN(C)CCOC(C)=O GOLSFPMYASLXJC-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229960003010 sodium sulfate Drugs 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 210000003537 structural cell Anatomy 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Coloring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Vynález sa týká zmesi Izotaktického polypropylénu s dusík obsahujúcim vinylovým kopolymérom, pričom kompozitný systém je vhodný na výrobu povrchovofarbíteiných vláken a fólií so zvýšenou světelnou stabilitou.The invention relates to a mixture of isotactic polypropylene with a nitrogen-containing vinyl copolymer, wherein the composite system is suitable for producing surface-colored fibers and films with enhanced light stability.
Na zlepšenie vyfarbiteinostl polypropylénových vláken, ktoré vykazujů nízku afinitu k farbivám, bolí navrhnuté rózne aditíva polymérneho typu. Jedná sa o zmesi polypropylénu s polyamidmi, polyamínotriazolmi, s kopolymérmi vinylpyrídínu, akrylonltrilu a pod., avšak váčŠinou sa u týchto zmesi prejavuje zhoršená spracovatefnosť pri zvlákňovacom procese.To improve the dyeability of polypropylene fibers having low affinity for dyes, various polymer-type additives have been proposed. These are mixtures of polypropylene with polyamides, polyaminotriazoles, with copolymers of vinylpyridine, acrylonitrile and the like, but these mixtures tend to exhibit poor processability in the spinning process.
Příčinou je nedostatečná kompatibilita přidávaných polymérnych modifikátorov s polypropylénom. Zlepšenie znášanlivosti s polypropylénom sa dosahuje u kopolymérov etylénu s N-vinylkarbazolom, aminoalkylakrylátmi alebo akrylamidom, nie sú však u vačšiny navrhovaných modifikátorov dostatečné vyhovujúce parametre zvlákňovania s polypropylénom a charakteristiky vyfarbovania vláken.This is due to the lack of compatibility of the added polymeric modifiers with polypropylene. Improvement of polypropylene compatibility is achieved with ethylene copolymers with N-vinylcarbazole, aminoalkyl acrylates or acrylamide, but with the proposed modifiers the satisfactory polypropylene spinning and fiber coloring characteristics are not sufficient.
Tento vynález vymedzuje výhodný postup modifikácie izotaktického polypropylénu pre aplikácie na tvarované výrobky so zlepšenou povrchovou farbitefnosťou a fotostabilitou.The present invention defines a preferred process for modifying isotactic polypropylene for applications to shaped articles with improved surface colorability and photostability.
Podstatou tohto vynálezu je zmes z izotaktického polypropylénu, vhodná pre výrobu farbitefných fólií a vláken, vyznačujúce sa tým, že sa skládá z 80 až 99 % hmotnostných izotaktického polypropylénu a 1 až 20 % hmotnostných statistického vínylověho kopolyméru, ktorý obsahuje opakujúce sa jednotky obecného vzorca AThe present invention provides a mixture of isotactic polypropylene suitable for the production of colorable films and fibers, characterized in that it is composed of 80 to 99% by weight of isotactic polypropylene and 1 to 20% by weight of a statistical vinyl copolymer containing repeating units of the general formula A
CH—CHoO = C-O-fCH2)2 N(R1J kde R1 označuje metylová alebo etylovú skupinu, opakujúce sa jednotky vzorca B —-(CHz—CHzJ — (B) a vzorca CCH-CHoO = CO-fCH 2 ) 2 N (R 1J where R 1 denotes a methyl or ethyl group, repeating units of formula B - (CH 2 - CH 2 -) (B) and formula C
CH —CH -
CHr.CH.
o=c-qc^h£ the c-qc = h ^ £
COWHAT
a připadne opakujúce sa jednotky obecného vzorca Dand optionally repeating units of formula (D)
(d) kde(d) where
R2 znamená metylová skupinu aR 2 is methyl and
R3 označuje vodíkový atom alebo metylovú skúpinu, pripravitelného reesterifikáciou 100 hmotnostných dielov kopolyméru etylénu (Bj s etylakrylátom (C) za použitia 10 až 300 hmotnostných dielov alkoholu obecného vzorca ROH alebo jeho esteru CH3(CH2)nCOOR, kde R podl'a jednotky A znamená skupinu (R1 jžN—CHz— CH2 a/alebo podía jednotky D 2,2,6,6-tetrametyl-4-piperidylovú alebo l,2,2,6,6-pentametyl-4-piperidylovú skupinu, n je 0 až 2, v roztoku aromatických rozpúšťadiel za přítomnosti bázických katalyzátorov, ako sú amidy alkalických kovov, pričom v kopolyméri obsahujúcom jednotky A, B a C je podiel jednotiek A a C 3 až 17 % molárnych a v kopolyméri obsahujúcom jednotky A, B, C a D je podiel jednotiek A a C 2 až 16 % molárnych a jednotiek D 1 až 15 % molárnych.R 3 denotes a hydrogen atom or a methyl group obtainable by re-esterification of 100 parts by weight of an ethylene copolymer (Bj with ethyl acrylate (C) using 10 to 300 parts by weight of an alcohol of formula ROH or its ester CH 3 (CH 2) n COOR) A represents a group (R 1, N-CH 2 -CH 2 and / or according to the unit D a 2,2,6,6-tetramethyl-4-piperidyl or 1,2,2,6,6-pentamethyl-4-piperidyl group, n is 0 to 2, in a solution of aromatic solvents in the presence of basic catalysts such as alkali metal amides, wherein in the copolymer containing units A, B and C the proportion of units A and C is 3 to 17 mol% and in the copolymer containing units A, B, C and D is the proportion of units A and C of 2 to 16 mol% and of the units D of 1 to 15 mol%.
Výsledný produkt po reesterifikácii, obsahujúci 0,5 až 3,5 % hmot. dusíka sa z roztoku izoluje vyzrážaním do vodného roztoku etylalkoholu. Po filtrácii vysušený produkt o priemernej číselnej molekulovej hmotnosti (Mnj výhodné v rozsahu 6 000 až 30 000 sa homogenizuje s izotaktickým polypropylénom a před zvlákňovaním alebo tvarováním na fólie sa polypropylénová zmes granuluje na vytlačovacom zariadení.The resulting product after re-esterification, containing 0.5 to 3.5 wt. The nitrogen is isolated from the solution by precipitation into an aqueous solution of ethyl alcohol. After filtration, the dried product having an average molecular weight (Mnj preferably in the range of 6,000 to 30,000) is homogenized with isotactic polypropylene and granulated on an extruder prior to spinning or film forming.
Kopolyméry etylénu s etylakrylátom, modifikované polyméranalogickou transformáciou, obsahujúce po reesterifikácii etylakrylátových jednotiek (s účinnosťou 25 až 70 percentj jednotky 2-(dialkylamíno)etylakrylátu, a připadne jednotky 2,2,6,6-tetrametyl alebo l,2,2,6,6-pentametyl-4-piperidylakrylátu vykazujú požadovaná technologickú znášanlivosť s polypropylénom.Copolymers of ethylene with ethyl acrylate, modified by polymer-analogue transformation, containing, after re-esterification of ethyl acrylate units (with an efficiency of 25 to 70 per cent of 2- (dialkylamino) ethyl acrylate unit and optionally 2,2,6,6-tetramethyl units or 1,2,2,6, 6-Pentamethyl-4-piperidyl acrylate show the desired technological compatibility with polypropylene.
Kopolyméry obsahujúce menej ako 0,8 % hmot. dusíka nezabezpečujú v polypropylénovej zmesi dostatočný efekt vyfarbitefnosti, pokial' sú přidávané do polypropylénu v rozsahu do 15 % hmot. Pri dávkovaní vo vyšších koncentráciach než 20 % hmot. produkty z týchto zmesí nedosahujú požadované mechanické vlastnosti.Copolymers containing less than 0,8% by weight of Nitrogen does not provide a sufficient coloring effect in the polypropylene blend when added to the polypropylene in the range of up to 15 wt. At dosages higher than 20 wt. the products of these mixtures do not achieve the desired mechanical properties.
Pre aplikácie na tvarované výrobky najma vlákna je výhodné, ked' sa polypropylénová zmes, obsahujúca kopolymér v množstve 4 až 12 % hmot. (s obsahom dusíka v kopolyméri výhodné v rozmedzí 1,2 až 7 % hmot.), zhomogenizuje s antioxidantami, príp. s prídavkom stearanu vápenatého alebo stearanu sodného.For applications on molded articles in particular fibers, it is preferred that the polypropylene composition containing the copolymer in an amount of 4 to 12 wt. (having a nitrogen content of the copolymer preferably in the range of 1.2 to 7% by weight), homogenizes with antioxidants, resp. with the addition of calcium stearate or sodium stearate.
Granulovaná zmes sa potom zvlákňuje z taveniny, s výhodou v inertnej atmosféře dusíka.The granular mixture is then melt-spun, preferably under an inert nitrogen atmosphere.
Vlákna alebo fólie podía tohto vynálezu vykazujú velmi dobrú afinitu voči kyslým farbivám pri povrchovom farbení, Vyfarbenie vláken a fólií je možno uskutočniť běžnými postupmi pri teplote 100 °C po dobu h vo vodných roztokoch obsahujúcich 2 až 4 °/o hmot. farbiva vzhfadom na hmotnost vláken alebo fólií, pri pomere hmotnosti farbeného výrobku ku kúpelu 1: 50.The fibers or films of the present invention exhibit very good affinity for acid dyes in surface dyeing. The dyeing of the fibers and films can be accomplished by conventional procedures at 100 ° C for h in aqueous solutions containing 2-4% w / w. colorants based on the weight of the fibers or sheets, at a weight ratio of dyed product to bath of 1:50.
Farbenie je výhodné uskutočniť za přítomnosti 1,5 % hmot. povrchovoaktívnych látok na báze reakčných produktov etylénoxidu a alkylfenolu a tiež výhodné za přídavku 2 % octanu amonného, alebo síranu sodného, alebo salicylanu sodného, vzhfadom na hmotnost vláken a za přídavku kyseliny mravčej pri nastavení acidity kúpela v rozmedzí hodnot pH 2,5 až 3,5.The dyeing is preferably carried out in the presence of 1.5 wt. surfactants based on the reaction products of ethylene oxide and alkylphenol, and also preferably with the addition of 2% ammonium acetate or sodium sulfate, or sodium salicylate, based on the fiber weight, and with the addition of formic acid when the acidity of the bath is adjusted to pH 2.5 to 3; 5th
Po vyfarbení sa vlákna alebo fólie vypierajú vo vodě a potom vo vodnom roztoku saponátu o konc. 0,1 až 0,2 % hmot. Vyfarbené vlákna vykazujú požadovaná stálost voči oderu a vypieraniu pri chemickom čistění a zvýšená stabilitu voči degradácii.After dyeing, the fibers or foils are washed in water and then in an aqueous detergent solution of conc. 0.1 to 0.2 wt. The dyed fibers exhibit the desired resistance to abrasion and scrubbing in dry cleaning and increased stability to degradation.
Příklad 1Example 1
Do reakčnej trojtubusovej banky o obsahuTo the reaction three-tube flask of contents
000 ml sa nadávkuje 135 g kopolyméru etylénu s etylakrylátom sušeného 5 h pri teplote 50 °C a tlaku 0,1 až 0,5 kPa, obsahujúceho 18 % hmot. etylakrylátovej zložky.135 ml of ethylene-ethylacrylate copolymer dried at 50 DEG C. under a pressure of 0.1 to 0.5 kPa and containing 18% by weight of ethyl acetate are metered in. ethylacrylate component.
Ďalej sa přidá 120 ml bezvodého N,N-dietyl-2-amínoetylalkoholu, 20 g 2,2,6,6-tetrametyl-4-hydroxypiperidínu a 300 ml bezvodého xylénu. Po rozpuštění kopolyméru sa pri teplote 70 °C přidá 3,74 g amidu lítneho a za miešania zmes reaguje pri teplote 132 až 135 C po dobu 12 h v inertnej atmosféře.120 ml of anhydrous N, N-diethyl-2-aminoethyl alcohol, 20 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine and 300 ml of anhydrous xylene are added. After dissolution of the copolymer, 3.74 g of lithium amide was added at 70 ° C and the mixture was stirred at 132-135 ° C for 12 h under inert atmosphere with stirring.
Po ochladení na teplotu 90 °C sa roztok kopolyméru po reakcii zriedi s 1 500 ml xylénu a vyzráža do etanolu. Odfiltrovaný produkt sa extrahuje po dobu 12 h roztokom etanolu (obsahujúcim 10 obj. dielov vody].After cooling to 90 ° C, the copolymer solution is diluted with 1500 ml of xylene after reaction and precipitated into ethanol. The filtered product is extracted for 12 h with an ethanol solution (containing 10 parts by volume of water).
Po premytí etanolom sa na vzduchu sušený produkt zbaví zbytkových rozpúšťadiel sušením za vákua 0,1 až 0,2 kPa pri teplote 50 °C. Priemerná číselná molekulová hmotnost produktu (18 000) je porovnatelná s Mn východiskového etylén-etylakrylátového kopolyméru.After washing with ethanol, the air-dried product is freed of residual solvents by drying under vacuum at 0.1 to 0.2 kPa at 50 ° C. The average molecular weight of the product (18,000) is comparable to the Mn of the starting ethylene-ethyl acrylate copolymer.
Kopolymér obsahujúci 1,3 % hmot. dusíka sa přidá v množstve 130 g k 1150 g práškovitého polypropylénu Tatren HPF (výrobok n. p. Slovnaft, ČSSR) a do zmesi sa přidá 20 g stearanu sodného a 1,3 g tris-(3,5242275Copolymer containing 1.3 wt. 130 g of nitrogen powder was added to 1150 g of powdered polypropylene Tatren HPF (manufactured by n. p. Slovnaft, Czechoslovakia) and 20 g of sodium stearate and 1.3 g of tris- (3.5242275) were added to the mixture.
-diterc.butyl-4-hydroxybenzyl) izokyanurátu s antioxidačným účinkom.-ditert-butyl-4-hydroxybenzyl) isocyanurate with antioxidant effect.
Zhomogenizovaná zmes sa granuluje pri teplote 230 °C a zvlákňuje na zariadení s priemerom závitnice 32 mm pri teplote zariadenia a hubicového bloku 260 °C (hubica 20 otvorov o príemere 0,5 mm) pri použití dávkovania 25 g/min,. (index toku 8,8 g/10 minúí) a navíjace] rýchlosti 600 m/min.The homogenized mixture is granulated at 230 ° C and spun on a 32 mm diameter screw machine at a machine temperature and a 260 ° C die block (20 mm 0.5 orifice nozzle) at a rate of 25 g / min. (flow index 8.8 g / 10 min) and a winding speed of 600 m / min.
Vydížené vlákna pri dížiacom pomere 1: : 3,5 vykazujú jemnost 107,7 dtex a pevnost 3,76 cN/dtex. Vlákna sa vyfarbujú pri pH 2,5 vo vodnom kúpeli obsahujúcom vzhladom na hmotnost vlákna 2 % farbiva Suminol fast.blue RP, 2 % povrchovoaktívnej látky (na báze polyetylénoxidu a alkylfenolu) a 1 % salicylanu sodného.The lined fibers at a 1:: 3.5 ratio have a fineness of 107.7 dtex and a strength of 3.76 cN / dtex. The fibers are stained at pH 2.5 in a water bath containing 2% by weight of the fiber 2% Suminol fast.blue RP, 2% surfactant (based on polyethylene oxide and alkylphenol) and 1% sodium salicylate.
Po 1 h farbenla pri 100 °C sa pozoruje vyčerpáme farbiva z kúpela. Rovnoměrné sýte vyfarbenie zostáva bez změny aj po působení 0,2 % hmot. roztoku dodecylsulfátu sodného po dobu 30 min pri teplote 60 °C. Pri urýchlenom stárnutí vláken (Xenotest) vykazuje modifikačná zložka porovnatelný stabilizačný efekt ako bis (2,2,6,6-tetrametyl-4-piperidyl)sebakát pri rovnakej koncentrácii (3,2.10 '3 mol/kg) tetrametylpiperidínových štruktúrnych článkov s fotostabilizačným účinkom.After 1 hour of dye at 100 ° C, the dyes from the bath are observed to be depleted. The uniform deep coloring remains unchanged even after treatment with 0.2 wt. of sodium dodecyl sulfate solution for 30 min at 60 ° C. In accelerated fiber aging (Xenotest), the modifying component exhibits a comparable stabilizing effect to bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate at the same concentration (3.2.10 -3 mol / kg) of tetramethylpiperidine structural cells with photostabilizing effect .
Příklad 2Example 2
Do raekčnej banky o obsahu 100 ml sa vloží 9 g etylénetylakrylátového kopolyméru (obsah etylakrylátu 34,7 % hmot.), 8 g sušeného N,N-dimetyl-2-amínoetylesteru kyseliny octovej, 1,1 g l,2,2,6,6-pentametyl-4-piperidylesteru kyseliny propiónovej a 20 mililitrov sušeného toluénu.To a 100 ml screening flask was charged 9 g ethylene ethyl acrylate copolymer (34.7 wt% ethyl acrylate), 8 g acetic acid N, N-dimethyl-2-aminoethyl ester, 1.1 g, 2.2.6, Propionic acid 6-pentamethyl-4-piperidyl ester and 20 ml of dried toluene.
Po rozpuštění pri teplote 90 °C sa přidá 0,12 g metanolátu sodného a 0,2 g lítiumamidu a reakčná zmes sa vyhrieva na teplotu 105 °C. Za miešania v inertne) atmosféře polyméranalogická reakcia prebieha po dobu 8 h a potom sa roztok zriedi prídavkom 70 ml toluénu a produkt sa izoluje vyzrázením do etanolu.After dissolution at 90 ° C, 0.12 g of sodium methanolate and 0.2 g of lithium amide are added and the reaction mixture is heated to 105 ° C. While stirring under an inert atmosphere, the polymer-analogous reaction is carried out for 8 hours and then the solution is diluted with 70 ml of toluene and the product is isolated by precipitation in ethanol.
Vysušený kopolymér (Mn 14 200, za použitia VPO) s obsahom dusíka 3,1 % hmot. v množstve 0, 6 g sa zmieša s 9,3 g práškovitého polypropylénu Tatren HPF, 0,1 g stearanu sodného a 0,01 g 2,6-diterc.butyl-4-metylfenolu.Dried copolymer (Mn 14,200, using VPO) with a nitrogen content of 3.1% by weight. in an amount of 0.6 g is mixed with 9.3 g of powdered polypropylene Tatren HPF, 0.1 g of sodium stearate and 0.01 g of 2,6-di-tert-butyl-4-methylphenol.
Připravená zmes sa homogenizuje pri teplote 210 °C v inertnej atmosféře dusíka. Z takto modifikovaného polypropylénu sa lisováním pri teplote 210 °C pripravia fólie o hrúbke 0,11 až 0,13 mm, ktoré sa vyfarbujú podťa postupu uvedeného v příklade 1. U vyfarbených fólií na sýty odtieň sa dosahuje dobrá stálost voči vypieraniu farbiva vo vodnom roztoku saponátu dodecylsulfátu sodného o koncentrácii 0,4 % hmot. pri teplote 60 °C počas 30 minút.The prepared mixture is homogenized at 210 ° C under an inert nitrogen atmosphere. Films having a thickness of 0.11 to 0.13 mm are prepared from the modified polypropylene by compression at 210 ° C and colored according to the procedure of Example 1. Good color fastness to dye wash in aqueous solution is achieved with dyed films for deep shade sodium dodecyl sulphate at a concentration of 0.4% by weight; at 60 ° C for 30 minutes.
Příklad 3Example 3
Do reakčnej banky o obsahu 2 000 ml sa vloží 150 ml bezvodého N,N-dieťyí-2-amínoetylalkoholu a 1,4 g lítia. Pri zahrievaní zmesi na teplotu 120. °C v inertnej atmosféře sa lítium postupné spotřebuje na vytvorenie lítnej soli.In a 2000 ml reaction flask was charged 150 ml of anhydrous N, N-diethyl-2-aminoethyl alcohol and 1.4 g of lithium. When the mixture is heated to 120 ° C under an inert atmosphere, the lithium is gradually consumed to form the lithium salt.
Do banky sa potom přidá 350 ml bezvodého xylénu, 22 g 2,2,6,6-tetrametyl-4-hydroxypiperidínu a 150 g etylén-etylakrylátového kopolyméru (obsah etylakrylátu 18 % hmot.) a pri postupnom zvyšovaní teploty po rozpuštění kopolyméru sa reakčná zmes za miešania zahrieva v rozmedzí teplot 132 až 136 °C po dobu 11 h.350 ml of anhydrous xylene, 22 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine and 150 g of ethylene-ethyl acrylate copolymer (18% by weight of ethyl acrylate) are then added to the flask and the reaction temperature is gradually increased after dissolution of the copolymer. with stirring, the mixture is heated at a temperature of 132-136 ° C for 11 h.
Po ochladení na teplotu 80 °C sa roztok zriedi přidáním 1 300 ml xylénu a produkt sa izoluje vyzrážaním do etanolu obsahujúceho 5 % obj. vody. Po vysušení na vzduchu a za vákua 0,1 až 0,5 kPa pri teplote 50 °C, po dobu 5 h, sa modifikovaný kopolymér, obsahujúci 1,44 % hmot. dusíka přidá v množstve 145 g k 1150 g polypropylénu Tatren HPF a do zmesi sa dalej přidá 25 g stearanu sodného a 1,35 g tris-(3,5-diterc.butyl-4-hydroxybenzyl) izokyanurátu.After cooling to 80 ° C, the solution is diluted by adding 1,300 ml of xylene and the product isolated by precipitation in ethanol containing 5% by volume. water. After drying in air and under a vacuum of 0.1 to 0.5 kPa at 50 ° C for 5 h, the modified copolymer containing 1.44 wt. Nitrogen is added in an amount of 145 g to 1150 g of polypropylene Tatren HPF and 25 g of sodium stearate and 1.35 g of tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate are added.
Připravená zmes sa zvlákňuje za podmienok uvedených v příklade 1. Vydížené vlákna pri dížiacom pomere 1: 3,5 o jemnosti 110,9 dtex sa vyfarbujú za analogických podmienok ako v příklade 1. Sýto vyfarbené vlákna vykazujú požadovanú stálost voči vypieraniu v roztoku dodecylsulfátu sodného o konc. 0,4 % hmot.The prepared blend is spun under the conditions of Example 1. The chopped fibers at a ratio of 1: 3.5 having a fineness of 110.9 dtex are dyed under analogous conditions to Example 1. The deep dyed fibers exhibit the desirable fastness to scrubbing in sodium dodecylsulfate solution. conc. 0.4 wt.
Vynález može nájsť široké použitie v chémii a spracovaní polymérov, pre výrobu povrchovo vyfarbiteťných tvarovaných polypropylénových výrobkov so zvýšenou světelnou stabilitou.The invention can be widely used in the chemistry and processing of polymers for the manufacture of surface-colorable molded polypropylene articles with enhanced light stability.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS846063A CS242275B1 (en) | 1984-08-09 | 1984-08-09 | Mixture of isotactic polypropylene suitable for dyeing foils and fibres production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS846063A CS242275B1 (en) | 1984-08-09 | 1984-08-09 | Mixture of isotactic polypropylene suitable for dyeing foils and fibres production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS606384A1 CS606384A1 (en) | 1985-08-15 |
| CS242275B1 true CS242275B1 (en) | 1986-04-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS846063A CS242275B1 (en) | 1984-08-09 | 1984-08-09 | Mixture of isotactic polypropylene suitable for dyeing foils and fibres production |
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| Country | Link |
|---|---|
| CS (1) | CS242275B1 (en) |
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1984
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| CS606384A1 (en) | 1985-08-15 |
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