NO792179L - PROCEDURE FOR THE MANUFACTURE OF LIGHT STABILIZED PHOSPHORUS POLYESTER - Google Patents
PROCEDURE FOR THE MANUFACTURE OF LIGHT STABILIZED PHOSPHORUS POLYESTERInfo
- Publication number
- NO792179L NO792179L NO792179A NO792179A NO792179L NO 792179 L NO792179 L NO 792179L NO 792179 A NO792179 A NO 792179A NO 792179 A NO792179 A NO 792179A NO 792179 L NO792179 L NO 792179L
- Authority
- NO
- Norway
- Prior art keywords
- phosphorus
- polyester
- acid
- groups
- ester
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 66
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000011574 phosphorus Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- -1 phosphoric acid triesters Chemical class 0.000 claims abstract description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 230000006641 stabilisation Effects 0.000 claims abstract description 11
- 238000011105 stabilization Methods 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002927 oxygen compounds Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 230000032050 esterification Effects 0.000 claims abstract description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001515 polyalkylene glycol Chemical group 0.000 claims abstract description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 10
- 125000003827 glycol group Chemical group 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 22
- 150000002148 esters Chemical class 0.000 abstract description 12
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 abstract description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 2
- QXFUBAAEKCHBQY-UHFFFAOYSA-N 3-[hydroxy(methyl)phosphoryl]propanoic acid Chemical compound CP(O)(=O)CCC(O)=O QXFUBAAEKCHBQY-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 16
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 12
- 239000000049 pigment Substances 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 150000003014 phosphoric acid esters Chemical class 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002334 glycols Chemical class 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical class COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- MGEISCKTUGVOHN-UHFFFAOYSA-N tris(2-hydroxyethyl) phosphate Chemical compound OCCOP(=O)(OCCO)OCCO MGEISCKTUGVOHN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PHGBTOBVWQJBKT-UHFFFAOYSA-N OC(=O)P(O)=O Chemical class OC(=O)P(O)=O PHGBTOBVWQJBKT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- JXNCBISRWFPKJU-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O JXNCBISRWFPKJU-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical class CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Abstract
Description
Fremgangsmåte til fremstilling avMethod for the production of
lysstabiliserte fosforholdige polyestere.light-stabilized phosphorous polyesters.
Oppfinnelsen vedrører en fremgangsmåte til fremstilling av matterte, lineære polyestere ved omsetning av The invention relates to a method for the production of matted, linear polyesters by conversion of
a) tereftalsyre eller dens dimetylestera) terephthalic acid or its dimethyl ester
b) et glykolb) a glycol
c) en fpsforholdig kjedeledd leverende forbindelse, idet dette kjedeledd utgjør inntil 15 vekt% referert c) an fps-proportional chain link supplying compound, this chain link making up to 15% by weight referred to
til den ferdige polyester ogto the finished polyester and
d) oksygenforbindelser av fosfor.d) oxygen compounds of phosphorus.
De i lengere tid kjente industrielt fremstilte polyestere har vanligvis en for de praktiske anvendelsers formål.god eller meget god lysbestandighet. De for det tekstile område anvendte syntetiske lineære polyestere på basis av tereftalsyre og glykoler, f.eks. polyetylentereftalat, og polybutylentéreftalatet har i form av fibre, tråder og folier likeledes en meget god lysbestandighet. Disse polyestere av tereftalsyre, som f.eks. poly-etylenteref talat kan ved innbygning av andre dikarboksylsyrer eller dioler modifiseres kjemisk, for for bestemte anvendelsesformål å få målrettede egenskapsendringer av f.eks. fibre, tråder eller folier. Foruten dikarboksylsyrer kan det også i polyestermolekylet kjemisk innbygges andre syrekomponenter med minst to syrefunksjoner som er istand til esterdannelse, f.eks. fosfonsyrer og fosfinsyrer. Innbygges grupper med fosfor-atomer i polyestermolekylet, så kan man fra en bestemt tilsetningsmengde eksempelvis få polyestertrådér og -fibre, som foruten en forbedret farvbarhet også er tungt oppflambare resp. selvslukkende. The long-known industrially produced polyesters usually have good or very good light fastness. The synthetic linear polyesters used for the textile area based on terephthalic acid and glycols, e.g. polyethylene terephthalate, and polybutylene terephthalate in the form of fibres, threads and foils also have very good light resistance. These polyesters of terephthalic acid, such as e.g. Polyethylene terephthalate can be modified chemically by incorporating other dicarboxylic acids or diols, in order to obtain targeted changes in properties for specific application purposes, e.g. fibers, threads or foils. In addition to dicarboxylic acids, other acid components with at least two acid functions that are capable of ester formation can also be chemically incorporated into the polyester molecule, e.g. phosphonic acids and phosphinic acids. If groups with phosphorus atoms are incorporated into the polyester molecule, then from a certain amount of addition, for example, polyester threads and fibers can be obtained, which, in addition to improved dyeability, are also highly flammable or self-extinguishing.
I tillegg til de fosforholdige kokomponenter kanIn addition to the phosphorus-containing co-components can
det anvendes andre polyester-modifiseringskomponenter, eksempelvis slike med sulfonatgrupper eller nitrogenholdige forbindelser for fremstilling av basisk eller surt farvbare polyestere (seH.Buttner, Angew. Makromol.Chem. 40/41, 57(1974)). Pillfattige, lett farvbare polyesterfibre og-tråder kan videre fremstilles under anvendelse av små mengder av permanent nettdannere eller temporære nettdannere. other polyester modifying components are used, for example those with sulfonate groups or nitrogen-containing compounds for the production of basic or acid dyeable polyesters (see H. Buttner, Angew. Makromol. Chem. 40/41, 57 (1974)). Low-pill, easily dyeable polyester fibers and threads can further be produced using small amounts of permanent net formers or temporary net formers.
Nå viser ofte modifiserte polyestere i forhold tilNow often shows modified polyesters compared to
de ikke modifiserte polymere en noe nedsatt lysbestandighet. Dette gjør seg f.eks. bemerket i en sterkere endring av de tekstile egenskaper av fibre og tråder frembragt av polyesteren, dvs. riv-fasthet og rivutvidelse avtar sterkt i avhengighet av belysnings-tiden. Grunnen kan ligge i de anderledes innkondenserte struktur-enheter av modifiseringskomponentene når disse er mer følsomme overfor fotokjemiske og fotooksidative resp. også hydrolytiske innvirkninger. the unmodified polymers have a somewhat reduced light resistance. This happens e.g. noted in a stronger change in the textile properties of fibers and threads produced by the polyester, i.e. tear resistance and tear expansion decrease strongly in dependence on the illumination time. The reason may lie in the differently condensed structural units of the modification components when these are more sensitive to photochemical and photooxidative resp. also hydrolytic effects.
Som matteringsmidler settes til polyestere vanligvis titandioksyd-pigmenter når det ikke ønskes noen glinsende fibre eller tråder. Det kan som pigmenter anvendes såvel anatas- som også rutil-typen, idet det for fibre og tråder vanligvis fore-trekkes anatas-typen, da de hårde rutil-pigmenter fører til en øket slitasje på trådføringsorganer og valser ved spinning og strekking. Det er kjent at titandioksyd-pigmenter befordrer lys-avbygning av mange polymere, samt av farvestoffer ved katalysert fotooksydasjon. Ved det ikke-modifiserte handelsvanlige polyetylentereftalat, som er blitt fremstilt over dimetyltereftalat er den fotokjemiske innvirkning av titandioksydpigmentene liten, dvs. det består praktisk talt ingen forskjeller i lysbestandighet av matterte fibre og tråder med de i praksis vanlig inntil 2 vekt% TiC^-innhold i forhold til umatterte fibre og tråder. As matting agents, titanium dioxide pigments are usually added to polyesters when no shiny fibers or threads are desired. Both the anatase and rutile types can be used as pigments, as the anatase type is usually preferred for fibers and threads, as the hard rutile pigments lead to increased wear on thread guiding devices and rollers during spinning and stretching. It is known that titanium dioxide pigments promote light degradation of many polymers, as well as of dyes by catalyzed photooxidation. In the case of the non-modified commercial polyethylene terephthalate, which has been produced over dimethyl terephthalate, the photochemical effect of the titanium dioxide pigments is small, i.e. there are practically no differences in the light resistance of matted fibers and threads with those normally used in practice up to 2 wt% TiC^ content in relation to unmatted fibers and threads.
Ved kjemisk modifisert polyetylentereftalat inntrer ofte ved anvendelse av TiC^-matteringsmidler en forsterket lys-nedbrytning, dvs. at de matterte fibre og tråder har en mindre lysbestandighet enn de tilsvarende umatterte fibre og tråder. Lysbestandigheten er derfor også avhengig av mengden av tilsatt Ti02_pigment, dvs. jo høyere matteringsgraden er, desto sterkere er lysnedbrytningen av den modifiserte polyester. En spesielt sterk avhengighet av lysbestandigheten av TiC^-innhold av fibre og tråder opptrer når heteroatomer er innbygd i polyesterkjeden og som er følsomme overfor fotooksydativ innvirkning.. Dette er eksempelvis tilfelle ved polyestere som inneholder fosforholdige kjedeledd. Tråder og fibre av lineære polyestere, som inneholder fosforholdige kjedeledd er kjent. Spesielt er det egnet organiske derivater av forskjellige syrer av fosfor, f.eks. fosfonsyre og dens estere (DAS 1.243.819, DOS 1.595.598) og fosfinsyre- og dens estere (DÅS 1.232;348, tysk patent 2.236.037). Fosfinsyrer kan statistisk medinnbygges i polyesterkjeden med i kjeden i ester-bindingen bundne fosforatomer i form av difosfinsyrer tilsvarende tysk patent 2.236.037 eller i form av karboksyfosfinsyrer tilsvarende DOS 2.346.787. Fosforatomet kan imidlertid også være sideveis, bundet til et polyester-kjedeledd, f.eks. i form av en fosfinoksyd-gruppe tilsvarende DOS 2.242.002. With chemically modified polyethylene terephthalate, an enhanced light degradation often occurs when TiC^ matting agents are used, i.e. the matted fibers and threads have a lower light resistance than the corresponding unmatted fibers and threads. The light fastness is therefore also dependent on the amount of added Ti02_pigment, i.e. the higher the degree of matting, the stronger the light degradation of the modified polyester. A particularly strong dependence of the light fastness on the TiC^ content of fibers and threads occurs when heteroatoms are incorporated into the polyester chain and are sensitive to photooxidative effects. This is, for example, the case with polyesters containing phosphorus-containing chain links. Threads and fibers of linear polyesters, which contain phosphorus-containing chain links are known. In particular, organic derivatives of various acids of phosphorus are suitable, e.g. phosphonic acid and its esters (DAS 1,243,819, DOS 1,595,598) and phosphinic acid and its esters (DÅS 1,232;348, German patent 2,236,037). Phosphinic acids can be incorporated statistically into the polyester chain with phosphorus atoms bound in the chain in the ester bond in the form of diphosphinic acids corresponding to German patent 2,236,037 or in the form of carboxyphosphinic acids corresponding to DOS 2,346,787. However, the phosphorus atom can also be laterally, bound to a polyester chain link, e.g. in the form of a phosphine oxide group corresponding to DOS 2,242,002.
Til grunn for oppfinnelsen ligger den oppgave å tilveiebringe lysstabilisatorer for polyestere med fosforholdige kjedeledd, som spesielt blokkerer den fotokjemiske aktivitet av Ti02~pigmenter og dessuten har en bare meget liten flyktighet under den under vakuum foregående polykondensasjonsprosess. Dessuten bør de være lette å håndtere og å dosere, ikke danne avleiringer i reaktoren, føre til termisk stabile og farvemessig gode sluttprodukter, ikke vanskeliggjøre gjenvinning av glykolet og ikke innføre i reaksjonsblandingen stoffer som forstyrrer pro-sessforløpet. The invention is based on the task of providing light stabilizers for polyesters with phosphorus-containing chain links, which in particular block the photochemical activity of Ti02~pigments and, moreover, have only a very low volatility during the preceding polycondensation process under vacuum. In addition, they should be easy to handle and to dose, not form deposits in the reactor, lead to thermally stable and color-wise good end products, not make recovery of the glycol difficult and not introduce into the reaction mixture substances that disturb the course of the process.
Det er nu funnet at en tilsetning av tungt flyktige estere av fosforsyre kan bevirke en lysstabilisering av de mot innvirkning av lys følsomme med titandioksyd matterte kopolyestere. Som generelle polyesterstabilisatorer til blokkering av omforestringskatalysatoren for formålet termostabilisering, er det i mange patentskrifter omtalt nøytrale og sure estere, f.eks. i DAS 1.152.25 9 og i DOS 2.154.5 03. De sure fosforsyreestere, det er bare delvis forestrede fosforsyrer, er riktignok ikke flyktige, har imidlertid betraktelige ulemper som polyester-tilsetnings-middel, da de som syrer befordrer dannelsen av dietylenglykol fra etylenglykol. Dette er uønsket som biprodukt, da det som diol likeledes innbygges i polyestermolekylet og negativt påvirker polyesteregenskapene f.eks. smeltepunktet. Dessuten forårsaker fosforsyre og dens sure ester spesielt ved kontinuerlig.produk-sjonsprosess uønskede avleiringer i reaktoren, ved den hurtige dannelse av tungtløselige fosfater og fører véd en overskytende anvendelse til agglomerering av Ti02-pigmentet når dette anvendes som matteringsmiddel. It has now been found that an addition of highly volatile esters of phosphoric acid can effect a light stabilization of the copolyesters matted with titanium dioxide which are sensitive to the effect of light. As general polyester stabilizers for blocking the transesterification catalyst for the purpose of thermostabilization, neutral and acidic esters are mentioned in many patent documents, e.g. in DAS 1.152.25 9 and in DOS 2.154.5 03. The acidic phosphoric acid esters, which are only partially esterified phosphoric acids, are admittedly not volatile, but have considerable disadvantages as polyester additives, as they, as acids, promote the formation of diethylene glycol from ethylene glycol. This is undesirable as a by-product, as the diol is likewise incorporated into the polyester molecule and negatively affects the polyester properties, e.g. the melting point. Moreover, phosphoric acid and its acid esters cause unwanted deposits in the reactor, especially in the case of a continuous production process, by the rapid formation of sparingly soluble phosphates and lead to an excess application to agglomeration of the TiO2 pigment when this is used as a matting agent.
De nøytrale alkylestere av fosforsyre reagerer riktignok også med de toverdige metallioner av omforestrihgs-katalysatoren nøyaktig som fosforsyren selv til tungt oppløselige metallfosfater, riktignok er reaksjonshastigheten av omsetningen med fosforsyreestrene betraktelige, dvs. størrelsesorden mindre, da denne ikke mer er hurtig ionereaksjon. Derfor er det under de anvendte driftsbetingelser de nøytrale estere, av nevnte art allerede merkbart flyktig, også anført i DOS 2.412.216. Ved en lysstabilisering av kopolyestrene er flyktighetsproblemet av den tilsatte stabilisatorforbindelse dessuten betraktelig forsterket da det må tilsettes en vesentlig høyere mengde av fosforsyreester enn det som ville være nødvendig for bare termbstabilisering av polyesteren. It is true that the neutral alkyl esters of phosphoric acid also react with the divalent metal ions of the transesterification catalyst exactly as phosphoric acid itself to poorly soluble metal phosphates, although the reaction rate of the reaction with the phosphoric acid esters is considerable, i.e. an order of magnitude smaller, as this is no longer a fast ion reaction. Therefore, under the operating conditions used, the neutral esters, of the aforementioned kind, are already noticeably volatile, also listed in DOS 2,412,216. In the case of light stabilization of the copolyesters, the volatility problem of the added stabilizer compound is also considerably increased as a significantly higher amount of phosphoric acid ester must be added than would be necessary for thermal stabilization of the polyester alone.
Det er nu funnet at alle ønskede fordeler for en lysstabilisering av kjemisk modifiserte polyestere oppnås, når etter omforestrings- eller forestringstrinnet eller under polykondensasjonsreaksjonen tilsettes til lysstabilisering.:som oksygenforbindelser av fosfor fosforsyretriestere som inneholder 1 eller 2 alkylgrupper med 1-4 C-atomer, samt samtidig 2 eller 1 alkylenglykol- eller polyalkylenglykol-grupper, idet alkylen-gruppene på sin side inneholder 2-4 C-atomer, og at polyesteren matteres med Ti02. It has now been found that all the desired advantages for a light stabilization of chemically modified polyesters are achieved, when after the transesterification or esterification step or during the polycondensation reaction are added for light stabilization.:as oxygen compounds of phosphorus phosphoric acid triesters containing 1 or 2 alkyl groups with 1-4 C atoms, and at the same time 2 or 1 alkylene glycol or polyalkylene glycol groups, the alkylene groups in turn containing 2-4 C atoms, and that the polyester is matted with Ti02.
Alkylenglykoler og polyalkylenglykoletere med 2-4 C-atomer pr. alkylengruppe er f.eks. etylenglykol, 1,2-propandiol, 1,3-propandiol, 1,2-butandiol, 1,4-butandiol samt deres di-, oligo- og polymere etere. Den foretrukne utførelsesform anvender blandinger av fosforsyretriestere som foruten 1 eller 2 lavere-alkylgrupper inneholder mono- til polyetylenglykolgrupper som ester-grupper. De ifølge oppfinnelsen anvendte blandede fosforsyreestere fremstilles fortrinnsvis ved omsetning av et surt mono-eller dialkylfosfat eller en blanding av disse med et alkylenoksyd med 2-4 C-atomer etter kjente fremgangsmåter uten anvendelse av et oppløsningsmiddel eller katalysator. Alkylenoksydet adderer seg til de frie hydroksylgrupper av de sure alkylfosfater under dannelse av 2-hydroksyalkyl-estergrupper. Alkylenoksyd-addisjonen forblir imidlertid ikke stående ved denne monoaddisjon, men så lenge reaksjonsblandingen reagerer surt ved ennu frie syregrupper, addrer alkylenoksydet seg også til de endeplasserte hydroksylgrupper av de allerede adderte alkylenoksyd-enheter (se Houben-Weyl, Methoden der Organischen Chemie, Stuttgart 1964, bind XII/ Alkylene glycols and polyalkylene glycol ethers with 2-4 C atoms per alkylene group is e.g. ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol as well as their di-, oligo- and polymeric ethers. The preferred embodiment uses mixtures of phosphoric acid triesters which, in addition to 1 or 2 lower alkyl groups, contain mono to polyethylene glycol groups as ester groups. The mixed phosphoric acid esters used according to the invention are preferably prepared by reacting an acidic mono- or dialkyl phosphate or a mixture thereof with an alkylene oxide with 2-4 C atoms according to known methods without the use of a solvent or catalyst. The alkylene oxide adds to the free hydroxyl groups of the acidic alkyl phosphates to form 2-hydroxyalkyl ester groups. However, the alkylene oxide addition does not remain standing in this monoaddition, but as long as the reaction mixture reacts acidic with still free acid groups, the alkylene oxide also adds to the end-positioned hydroxyl groups of the already added alkylene oxide units (see Houben-Weyl, Methoden der Organischen Chemie, Stuttgart 1964 , volume XII/
2, side 3 07). Derved oppstår polyalkylenglykoletere som ester-grupper av forskjellige kjedelengder. Når mot slutten av reak-sjonen konsentrasjonen av syregruppene avtar sterkt, danner det seg dessuten bare monoaddisjonsprodukter, som er påvisbare analytisk ved forsåpning og gasskromatografiske bestemmelser i mengder på noen vekt%. Alkylenoksydaddisjonen fortsetter sålenge inntil den dannede fosforsyreester-blanding har et syretall mindre enn 1, dvs. praktisk talt ikke opptar mer alkylenoksyd. Syre-tallet (SZ) er definert som den mengde kaliumhydroksyd i mg som er nødvendig til nøytralisering av 1 g stoff.(se Rompp, Chemie Lexikon, 6, opplag, Stuttgart 1966, bind II, spalte 2037/8). 2, page 3 07). This results in polyalkylene glycol ethers as ester groups of different chain lengths. When, towards the end of the reaction, the concentration of the acid groups decreases strongly, only monoaddition products are formed, which are detectable analytically by saponification and gas chromatographic determinations in amounts of a few weight%. The alkylene oxide addition continues until the formed phosphoric acid ester mixture has an acid number less than 1, i.e. practically does not take up more alkylene oxide. The acid number (SZ) is defined as the quantity of potassium hydroxide in mg which is necessary to neutralize 1 g of substance. (see Rompp, Chemie Lexikon, 6, edition, Stuttgart 1966, volume II, column 2037/8).
De ved den foretrukne fremstillingsfremgangsmåte ifølge oppfinnelsen anvendte blandede fosforsyretriestere dannede oligo-og polyalkylenglykoletergrupper bevirker den fordel at den tilsatte stabilisator under polyester-polykondensasjonsprosessen bare har en meget liten flyktighet, og således ligger det (analytisk bestembare) fosfor-innhold i polyester bare litt under det på The oligo- and polyalkylene glycol ether groups formed by the mixed phosphoric acid triesters used in the preferred production method according to the invention have the advantage that the added stabilizer during the polyester polycondensation process only has a very low volatility, and thus the (analytically determinable) phosphorus content in polyester is only slightly below the on
grunn av den anvendte mengde beregnede.due to the amount used calculated.
De ved fremgangsmåten ifølge oppfinnelsen som lys-stabilisator anvendte blandede fosforsyreestere kan også fremstilles på annen måte enn den omtalte, som er en foretrukket ut-førelsesform. Eksempelvis kan mono- eller dialkylfosforsyrekloridene omsettes med glykoler resp. blandinger av tjlykoler under tilsetning, av et tertiært amin som base til fosforsyretriestere. Deretter The mixed phosphoric acid esters used as light stabilizer in the method according to the invention can also be produced in a different way than the one mentioned, which is a preferred embodiment. For example, the mono- or dialkyl phosphoric acid chlorides can be reacted with glycols or mixtures of tjlycols during addition, of a tertiary amine as a base for phosphoric acid triesters. Then
må imidlertid det;dannede amin-hydroklorid adskilles kvantitativt, da det ellers opptret forstyrrelser ved polyesterfremstillingen og polyesteregenskapene påvirkes negativt. På lignende måte kan ved reaksjon av fosforoksyklorid, POCI3, med glykoler, polyglykoler eller blandinger av disse og samtidig nærvær av alkanoler, eller også i et etterfølgende reaksjonstrinn ved samtidig nærvær av en base som klorhydrogenakseptor, fremstilles de ovenfor omtalte blandede fosforsyretriestere ifølge oppfinnelsen (sml. Japansk patent nr. 64.30.154; CA. 62, 11737a). En ytterligere mulighet for deres fremstilling består i en omforestringsreaksjon av et lavere trialkylfosfat med glykoler. Denne reaksjon foregår også ved høyere temperaturer uten en katalysator bare partielt og meget langsomt under samtidig partiell hydrolyse. For en brukbar omfor- however, the amine hydrochloride formed must be separated quantitatively, as otherwise disturbances would occur during the polyester production and the polyester properties would be negatively affected. In a similar way, by reacting phosphorus oxychloride, POCI3, with glycols, polyglycols or mixtures thereof and the simultaneous presence of alkanols, or also in a subsequent reaction step with the simultaneous presence of a base as a chlorine hydrogen acceptor, the above-mentioned mixed phosphoric acid triesters according to the invention can be prepared (cf. .Japanese Patent No. 64.30.154; CA. 62, 11737a). A further possibility for their preparation consists in a transesterification reaction of a lower trialkyl phosphate with glycols. This reaction also takes place at higher temperatures without a catalyst only partially and very slowly during simultaneous partial hydrolysis. For a usable conversion
estringsreaksjon med høyere alkoholer resp. glykoler og polyglykoler er det derfor nødvendig med basiske katalysatorer (se Houben-Weyl, Methoden der Organischen Chemie, Stuttgart 1964, bind XII/2, side 371). Til anvendelse av således fremstilte blandede fosforsyretriestere som polyester-stabilisatorer må esterification reaction with higher alcohols resp. glycols and polyglycols, basic catalysts are therefore necessary (see Houben-Weyl, Methoden der Organischen Chemie, Stuttgart 1964, volume XII/2, page 371). For the use of thus produced mixed phosphoric acid triesters as polyester stabilizers must
de basiske tilsetningsmidler på forhånd.fjernes resp. adskilles fra reaksjonsblandingen. the basic additives in advance. are removed resp. is separated from the reaction mixture.
I det allerede ovenfor nevnte DAS 1.152.259 er det som polyester^stabilisator for stabilisering etter omforestringen av dimetyltereftalat oppført "tris-(2hydroksyetyl)-fosfat". Denne forbindelse har imidlertid ved en anvendelse til lysstabilisering av modifiserte polyestere vesentlige ulemper. Da den har tre endeplasserte primære hydroksylgrupper, kan den ved polykondensasjonsprosessen reagere som trifunksjonell forbindelse og innbygges i polyesteren som forgrenings- respå nettdannelsespunkt (sml. M.C.St.Cyr, SPE Transactions 1, nr. 1, 47-51(1961)). Dette fører som bekjent alt etter mengde av tilsatt trifunksjonelle forbindelser til modifisert polyestere med tydelig endrede egenskaper, f.eks. en høyere smelteviskositet, mindre fasthet og høyere tverrsprøhet av trådene, alle egenskaper som bare ønskes i spesialtilfeller som polyester-egenskaper. De ved fremgangsmåten ifølge oppfinnelsen anvendte stabilisatorer er imidlertid med hensyn til hydroksylgruppen mono- eller bifunksjonelle, In the already mentioned DAS 1,152,259, "tris-(2-hydroxyethyl)-phosphate" is listed as polyester stabilizer for stabilization after the transesterification of dimethyl terephthalate. However, this compound has significant disadvantages when used for light stabilization of modified polyesters. As it has three end-placed primary hydroxyl groups, it can react as a trifunctional compound during the polycondensation process and be incorporated into the polyester as a branching or network formation point (cf. M.C.St.Cyr, SPE Transactions 1, no. 1, 47-51(1961)). As is well known, this leads, depending on the amount of added trifunctional compounds, to modified polyesters with clearly changed properties, e.g. a higher melt viscosity, less firmness and higher transverse brittleness of the threads, all properties that are only desired in special cases such as polyester properties. However, the stabilizers used in the method according to the invention are mono- or bifunctional with respect to the hydroxyl group,
kan altså innbygges i. den lineære polyesterkjede, eller befinne seg som endegruppe ved polyestermolekylet. På grunn av den mindre stabilisatorkonsentrasjon inntrer heller praktisk talt ingen forstyrrelser av polykondensasjonsreaksjonen ved kjedeav-brudd. can therefore be built into the linear polyester chain, or be found as an end group at the polyester molecule. Because of the smaller stabilizer concentration, there is also practically no disruption of the polycondensation reaction in the event of chain termination.
Ved en fremstilling av "tris-(2-hydroksyetyl)-fosfat" ved etylenoksyd-addisjon til fosforsyre kan av de ovenfor nevnte grunner ikke fåes;noen ren, definert forbindelse, da polyetylen-glykoleter-enheter oppstår av forskjellige kjedelengder som ester-grupper. Derved har denne stabilisator i forhold til blandings-esteren den ekstra ulempe med et betraktelig mindre fosforinnhold i molekylet, således at tilsvarende må det tilsettes en større mengde stabilisator til polyesteren, når det for oppnåelse av den ønskede stabiliseringseffekt er nødvendig med en bestemt fosfor-konsentrasjon i polyesteren. Derved kan da de ovennevnte ulemper ved trifunksjonell forbindelse opptre forsterket. In the preparation of "tris-(2-hydroxyethyl)-phosphate" by the addition of ethylene oxide to phosphoric acid, for the reasons mentioned above, no pure, defined compound can be obtained, as polyethylene glycol ether units arise from different chain lengths as ester groups . Thereby, compared to the mixed ester, this stabilizer has the additional disadvantage of a considerably lower phosphorus content in the molecule, so that a correspondingly larger amount of stabilizer must be added to the polyester, when a specific phosphorus concentration is required to achieve the desired stabilization effect in the polyester. Thereby, the above-mentioned disadvantages of a trifunctional connection can appear amplified.
De for fremstilling av fosforsyrétriesteren anvendte sure alkylfosfater er fortrinnsvis metylfosfater, dvs. monometylfosfat, dimetylfosfat eller også blandinger av begge. Det kan imidlertid også anvendes etyl-, propyl- eller butylfosfater. Disse sure alkylfosfater kan eksempelvis fremstilles ved omsetning av en polyfosforsyre med bestemt P20^-inrihold med en bestemt beregnet mengde ay en alkanol med 1-4 C-atomer, fortrinnsvis med metanol. Ved pksydasjon av dialkylfosfiter til dialkylfos-, fater kan det likeledes fåes utgangsforbindelser for de blandede fosforsyretriestere. The acidic alkyl phosphates used for the production of the phosphoric acid triester are preferably methyl phosphates, i.e. monomethyl phosphate, dimethyl phosphate or also mixtures of both. However, ethyl, propyl or butyl phosphates can also be used. These acidic alkyl phosphates can, for example, be prepared by reacting a polyphosphoric acid with a certain P20^ content with a certain calculated amount of an alkanol with 1-4 C atoms, preferably with methanol. By oxidation of dialkyl phosphites to dialkyl phosphates, starting compounds for the mixed phosphoric acid triesters can also be obtained.
De for addisjon til de sure alkylfosfater anvendte alkylenoksyder kan være etylenoksyd, propylenoksyd eller butylen-oksyd. Fortrinnsvis anvendes etylenoksyd. The alkylene oxides used for addition to the acid alkyl phosphates can be ethylene oxide, propylene oxide or butylene oxide. Ethylene oxide is preferably used.
Mengden av den til lysstabilisering av fosforholdige kopolyestere tilsatte stabilisatorer ifølge oppfinnelsen avhenger på den ene side av type og mengde anvendt modifiseringskomponenter og for det annet av matteringsgraden av polyesteren, dvs. hvor meget Ti02_pigment er inkorporert i polyesteren, samt av krystall-formen av titandioksyd og dets fremstillingsmåte. Ved kjemiske modifiseringer av tereftalsyre-polyestere kan det i praksis anvendes inntil ca. 15 vekt% av en kokomponent, referert til den ferdige polyester, for ennå å oppnå tilstrekkelig høyt smeltende polyestere. The quantity of the stabilizers according to the invention added for light stabilization of phosphorous copolyesters depends on the one hand on the type and amount of modification components used and on the other hand on the degree of matting of the polyester, i.e. how much Ti02_pigment is incorporated in the polyester, as well as on the crystal form of titanium dioxide and its method of manufacture. In the case of chemical modifications of terephthalic acid polyesters, up to approx. 15% by weight of a cocomponent, referred to the finished polyester, in order to still obtain sufficiently high-melting polyesters.
TiC^-matteringsmiddel anvendes ved polyester-fibreTiC^ matting agent is used with polyester fibres
og -tråder i mengder fra ca. 0,04 til ca. 2,0 vekt%. Begge krever selvsagt den tilsvarende variasjon i de tilsatte stabili-satormengder. For stabiliseringsvirkningen er hovedsakelig den tilsatte mengde ay femvérdig fosfor utslagsgivende. Derfor må også fosforinnholdet av stabilisator-forbindelsen tas hensyn til. and threads in amounts from approx. 0.04 to approx. 2.0% by weight. Both naturally require the corresponding variation in the amounts of stabilizer added. The stabilizing effect is mainly determined by the added amount of pentavalent phosphorus. Therefore, the phosphorus content of the stabilizer compound must also be taken into account.
Jo høyere innhold: av alkylgrupper, spesielt av metylgrupper,The higher the content: of alkyl groups, especially of methyl groups,
desto høyere er fosfor-innholdet av blandingsesterén og desto mindre stabilisator kreves i polyesteren. De anvendte stabilisa-tormengder refereres derfor til fosforinnholdet som herved tilsettes polyesteren. Dette kan ligge i området fra 10 ppm til 800 ppm fosfor, fortrinnsvis 20-800 ppm fosfor, spesielt imidlertid ved de mest praktiske anvendelsesformål mellom 30 og 300 ppm fosfor. Derved er fosfor-innholdene som stammer fra de fosforholdige kjedeledd i polyesteren ikke med-innberegnet. the higher the phosphorus content of the mixed ester and the less stabilizer required in the polyester. The amounts of stabilizer used are therefore referred to the phosphorus content that is added to the polyester. This can lie in the range from 10 ppm to 800 ppm phosphorus, preferably 20-800 ppm phosphorus, especially however for the most practical purposes of application between 30 and 300 ppm phosphorus. Thereby, the phosphorus contents originating from the phosphorus-containing chain links in the polyester are not taken into account.
Ved siden av tereftalsyre og de ovennevnte,fosfor holdige forbindelser som polyester-modifiseringsmiddel kan det som glykoler anvendes polymetylenglykoler med 2-10 C-atomer, men også cykliske glykoler som 1,4 cyklohexandimetanol og lignende forbindelser. Fortrinnsvis anvendes etylenglykol og butylenglykol. In addition to terephthalic acid and the above-mentioned phosphorus-containing compounds as polyester modifiers, glycols can be used polymethylene glycols with 2-10 C atoms, but also cyclic glycols such as 1,4 cyclohexanedimethanol and similar compounds. Ethylene glycol and butylene glycol are preferably used.
(= 1,4-butandiol).(= 1,4-butanediol).
Fordelene ifølge oppfinnelsen fremgår av følgende tabeller 1 og 2. Her er lysbestandigheten av polyetylentereftalat-filamentgarn sammenlignet, nemlig umodifisert polyetylentereftalat (PET) og med forskjellige fosforholdige kokomponenter modifisert polyetylentereftalat uten og med lysstabilisatorer. The advantages according to the invention can be seen from the following tables 1 and 2. Here the light fastness of polyethylene terephthalate filament yarn is compared, namely unmodified polyethylene terephthalate (PET) and modified polyethylene terephthalate with different phosphorus-containing co-components without and with light stabilizers.
Forklaringer til tabellene i detalj. Explanations to the tables in detail.
Her betyr:Here means:
(1) Belystningsundersøkelsen foregikk i et Xenotest-apparat fra firmaet Quarzlampen GmbH, Hanau, type Xenotest 450, ved 65% relativ luftfuktighet og en prøveromstemperatur fra 30 til 35°C. Temperaturen av selve prøvene, dvs. sorttavletemperaturen ("black panel temperature") utgjorde ca. 40°C. (2) Vekt% av modifiseringskomponentene ér referert til innhold i ferdig polyester. (3) Det i polyestrene under fremstillingsprosessen inn- arbeidede TiC^-pigment av anatas-typen er "Kronos AD" fra Kronos-Titan-GmbH, Leverkusen. Vekt% refererer seg til innholdet i ferdig polyester. (4) Vendeløpstimer: Belysningen foregikk i vendeløp (dag-natt-rytme), således at den rene belyshingstid utgjorde bare 50% av prøveløpstiden. (5) RRF betyr restrivfasthet, RRD betyr restrivutvidelse, nemlig angitt i prosent referert til utgangsrivfasthet og utgangsrivutvidelse. (6) Samtlige polyetylentereftalat(PET)-polyestere ble fremstilt etter dimetyltereftalat-omforestringsfrem-gangsmåten med etylenglykol, idet eventuelt den fosforholdige modifiseringskomponent ble tilsatt etter omforestringstrinnet. Omforestrings-katalysator: Mn(II)-acetat Polykondensasjons-katalysator: Sb9072+ Termostabilisator til blokkering av Mn : H-^PO^ ; (bare ved de uten tilsetning av fosforsyreester fremstilte polyestere). Fosforsyre (7) og (8) ble tilsatt etter omforestringstrinnet. (7) Som fosforsyreester ble det anvendt et produkt som ble dannet av en blanding av mono- og dimetylfosfat ved omsetning med etylenoksyd inntil et syre tall <-0,5 og hadde et fosforinnhold på 11,1 vekt%. Som fosforsyreester ble det anvendt produkter som ble dannet av monometylfosfat, CH^O-P^O) (OH^/ ved omsetning med etylenoksyd inntil et syrétall <0,5 og hadde et fosforinnhold på 7,2 vekt% resp. 7,7 vekt%. (9) iflg. DAS 2.346.787 (10) (1) The lighting test took place in a Xenotest apparatus from the company Quarzlampen GmbH, Hanau, type Xenotest 450, at 65% relative humidity and a test room temperature of 30 to 35°C. The temperature of the samples themselves, i.e. the black panel temperature, was approx. 40°C. (2) Weight % of the modification components is referred to content in finished polyester. (3) That in the polyesters during the manufacturing process worked TiC^ pigment of the anatase type is "Kronos AD" from Kronos-Titan-GmbH, Leverkusen. Weight% refers to the content of finished polyester. (4) Reversing hours: The lighting took place in reversing (day-night rhythm), so that the pure lighting time constituted only 50% of the test run time. (5) RRF means residual tear strength, RRD means residual tear expansion, namely stated in percentages referred to initial tear resistance and initial tear expansion. (6) All polyethylene terephthalate (PET) polyesters were produced according to the dimethyl terephthalate transesterification process with ethylene glycol, with the phosphorus-containing modifying component possibly being added after the transesterification step. Transesterification catalyst: Mn(II)-acetate Polycondensation catalyst: Sb9072+ Thermostabilizer to block Mn : H-^PO^ ; (only in the case of polyesters produced without the addition of phosphoric acid ester). Phosphoric acid (7) and (8) were added after the transesterification step. (7) As phosphoric acid ester, a product was used which was formed from a mixture of mono- and dimethyl phosphate by reaction with ethylene oxide up to an acid number <-0.5 and had a phosphorus content of 11.1% by weight. As phosphoric acid ester, products were used which were formed from monomethyl phosphate, CH^O-P^O) (OH^/ by reaction with ethylene oxide up to an acid number <0.5 and had a phosphorus content of 7.2% by weight or 7.7% by weight. (9) according to DAS 2.346 .787 (10)
iflg. tysk patent 2.236.037 according to German patent 2,236,037
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2828463A DE2828463C2 (en) | 1978-06-29 | 1978-06-29 | Process for the production of linear, light-stabilized polyesters matted with TiO2 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO792179L true NO792179L (en) | 1980-01-03 |
Family
ID=6043048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO792179A NO792179L (en) | 1978-06-29 | 1979-06-28 | PROCEDURE FOR THE MANUFACTURE OF LIGHT STABILIZED PHOSPHORUS POLYESTER |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0006603B1 (en) |
| JP (1) | JPS557888A (en) |
| AT (1) | ATE774T1 (en) |
| BR (1) | BR7904113A (en) |
| DD (1) | DD144552A5 (en) |
| DE (2) | DE2828463C2 (en) |
| DK (1) | DK274579A (en) |
| ES (1) | ES481810A1 (en) |
| FI (1) | FI792034A (en) |
| NO (1) | NO792179L (en) |
| PT (1) | PT69846A (en) |
| RO (1) | RO78142A (en) |
| ZA (1) | ZA793251B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3300315A1 (en) * | 1983-01-07 | 1984-07-12 | Dynamit Nobel Ag, 5210 Troisdorf | METHOD FOR PRODUCING LIGHT-COLORED POLYESTERS USING TITANIUM CATALYSTS |
| IT1217348B (en) * | 1988-03-23 | 1990-03-22 | Enichem Sintesi | LINEAR COPOLYESTER CONTAINING PHOSPHORUS, PROCEDURE FOR ITS PREPARATION AND USE AS A FIRE-RESISTANT AGENT |
| US5145941A (en) * | 1991-01-04 | 1992-09-08 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| US5151494A (en) * | 1991-01-04 | 1992-09-29 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| US5180793A (en) * | 1991-12-31 | 1993-01-19 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| JP5174980B1 (en) | 2012-06-12 | 2013-04-03 | ニチアス株式会社 | Soundproof cover for automobile and method for producing soundproof cover for automobile |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB769220A (en) * | 1953-09-30 | 1957-03-06 | Du Pont | Polyglycol terephthalates |
| US3097184A (en) * | 1958-05-31 | 1963-07-09 | Hoechst Ag | Modified, phosphorus-containing polyester resins and process for preparing same |
| DD102714A1 (en) * | 1973-03-15 | 1973-12-20 | ||
| DE2412216B2 (en) * | 1974-03-14 | 1979-12-13 | Davy International Ag, 6000 Frankfurt | Process for the production of linear polyesters |
-
1978
- 1978-06-29 DE DE2828463A patent/DE2828463C2/en not_active Expired
-
1979
- 1979-06-22 ES ES481810A patent/ES481810A1/en not_active Expired
- 1979-06-24 DD DD79213937A patent/DD144552A5/en unknown
- 1979-06-25 AT AT79102103T patent/ATE774T1/en active
- 1979-06-25 DE DE7979102103T patent/DE2962332D1/en not_active Expired
- 1979-06-25 EP EP79102103A patent/EP0006603B1/en not_active Expired
- 1979-06-26 RO RO7997962A patent/RO78142A/en unknown
- 1979-06-27 FI FI792034A patent/FI792034A/en not_active Application Discontinuation
- 1979-06-28 DK DK274579A patent/DK274579A/en not_active Application Discontinuation
- 1979-06-28 JP JP8082379A patent/JPS557888A/en active Pending
- 1979-06-28 NO NO792179A patent/NO792179L/en unknown
- 1979-06-28 PT PT69846A patent/PT69846A/en unknown
- 1979-06-28 BR BR7904113A patent/BR7904113A/en unknown
- 1979-06-29 ZA ZA793251A patent/ZA793251B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2828463C2 (en) | 1980-08-28 |
| DE2828463B1 (en) | 1979-12-13 |
| FI792034A (en) | 1979-12-30 |
| RO78142A (en) | 1982-02-01 |
| EP0006603B1 (en) | 1982-03-24 |
| DD144552A5 (en) | 1980-10-22 |
| ATE774T1 (en) | 1982-04-15 |
| ES481810A1 (en) | 1980-02-16 |
| ZA793251B (en) | 1980-07-30 |
| PT69846A (en) | 1979-07-01 |
| DK274579A (en) | 1979-12-30 |
| EP0006603A1 (en) | 1980-01-09 |
| JPS557888A (en) | 1980-01-21 |
| DE2962332D1 (en) | 1982-04-29 |
| BR7904113A (en) | 1980-03-25 |
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