CH575476A5 - Flameproof regenerated cellulose - contg. substituted cyclo-diphosphazans as flame inhibitors - Google Patents
Flameproof regenerated cellulose - contg. substituted cyclo-diphosphazans as flame inhibitorsInfo
- Publication number
- CH575476A5 CH575476A5 CH193474A CH193474A CH575476A5 CH 575476 A5 CH575476 A5 CH 575476A5 CH 193474 A CH193474 A CH 193474A CH 193474 A CH193474 A CH 193474A CH 575476 A5 CH575476 A5 CH 575476A5
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- flame
- radical
- cellulose
- compound
- Prior art date
Links
- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 27
- 239000003112 inhibitor Substances 0.000 title 1
- 239000001913 cellulose Substances 0.000 claims abstract description 21
- 229920002678 cellulose Polymers 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012991 xanthate Substances 0.000 claims abstract description 5
- -1 alkyl radical Chemical class 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 14
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- CPEONABTMRSIKA-UHFFFAOYSA-N 1,4$l^{2}-oxazinane Chemical compound C1COCC[N]1 CPEONABTMRSIKA-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 6
- 150000002431 hydrogen Chemical group 0.000 claims 4
- 239000002244 precipitate Substances 0.000 claims 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000011888 foil Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 4
- 125000002373 5 membered heterocyclic group Chemical group 0.000 abstract 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011044 quartzite Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ISJBQSJDQZLCSF-UHFFFAOYSA-N (4-chlorophenyl)azanium;chloride Chemical compound [Cl-].[NH3+]C1=CC=C(Cl)C=C1 ISJBQSJDQZLCSF-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6587—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having two phosphorus atoms as ring hetero atoms in the same ring
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Flame-proof regenerated cellulose contg. as flame-proofing agent a cpd. of the formula (I): (where Y is =O or =S; R = cyclohexyl, a phenyl gp, opt. substd. with up to 3 substs. selected from 1-3 Cl ats, 1 Br in p-posn. and/or 1-3 alkyl or alkoxy gps. each contg. 1-4C atoms and is not >4C in total, or when Y = S, also CH3; R2 is a gp. of formula: R3 = alkyl of 1-4C, R4 beta alkyl or 1-12C, cyclohexyl or an opt. substd. phenyl grp. as defined for R, or -NR3R4 together form a 5 or 6 membered heterocyclic ring, provided that when simultaneously Y = O, R3 = H and R1 = phenyl or substd. phenyl, then R4 is an opt. substd. phenyl). The flame-proofed cellulose is obtd. by pptg. regenerated cellulose from a soln. contg. cpd. (I). Pref. the regenerated cellulose is pptd. from a cellulose xanthate soln. contg. 15-25 wt. % of cpd. (I) w.r.t. alpha-cellulose. Other flame-proofing agents can be present, pref. also 10-90 wt. %. (esp. 15-60 wt. %) of a reaction prod. of phosphornitrile chloride and neopentyl glycol (w.r.t. the total amt. of flame proofing agents). The regenerated cellulose can be prod. in the form of fibres or foils in conventional manner by passing the cellulose soln. contg. flame-proofing agents through fine nozzles or slits into a pptn.-bath.
Description
Die vorliegende Erfindung betrifft flammfest ausgerüstete regenerierte Cellulose, welche dadurch gekennzeichnet ist, dass diese als flammfest machende Verbindung eine solche der Formel
EMI1.1
worin R1 einen Alkylrest mit 1-12 C-Atomen, Cyclohexyl, einen Phenylrest, der gegebenenfalls durch 1-3 Chloratome, 1-3 Alkyl- oder Alkoxyreste mit zusammen höchstens 6 C-Atomen, wobei der einzelne Alkyl- oder Alkoxyrest höchstens 4 C-Atome aufweist und/oder ein Bromatom in orthooder para-Stellung substituiert ist und höchstens 3 Substituenten trägt, R2 Chlor,
EMI1.2
oder OR5, R3 Wasserstoff, Methyl oder Äthyl, R4 eine der Bedeutungen von Rl, oder R3 und R4 zusammen, gegebenenfalls über ein weiteres Heteroatom, zu einem heterocyclischen Ring verbunden sind, und R5 einen Alkylrest mit 1-12 C-Atomen, Cyclohexyl, einem Phenylrest,
der gegebenenfalls durch 1-5 Chloratome, 1-5 Bromatome und/oder 1-3 Alkyloder Alkoxyreste mit zusammen höchstens 9 C-Atomen, wobei der einzelne Alkyl- oder Alkoxyrest höchstens 9 C-Atome aufweist, substituiert ist, bedeuten.
Bevorzugt ist flammfest ausgerüstete regenerierte Cellulose, welche dadurch gekennzeichnet ist, dass diese eine flammfest machende Verbindung der Formel
EMI1.3
enthält, worin R'1 einen Methylrest, Cyclohexyl, einen Phenylrest, der gegebenenfalls durch 1 oder 2 Chloratome, einen Al.
kyl- oder Alkoxyrest mit 1-4 C-Atomen und/oder ein.Brom- atom in ortho- oder para-Stellung substituiert ist, und höchstens 2 Substituenten trägt, R'2 Chlor,
EMI1.4
oder -OR'5, R'3 Wasserstoff, Methyl oder Äthyl, R'4 eine der Bedeutungen von R'l, oder R'3 und R'4 zusammen mit dem Stickstoffatom einen Piperidino-, Morpholino- oder Pyrrolidinoring bildern, und R'5 einen Alkylrest mit 1-6 C-Atomen, Cyclohexyl, einen Phenylrest, der gegebenenfalls durch 1-3 Chloratome, 1-3 Bromatome und/oder einen Alkyl- oder Alkoxyrest mit 1-4 C-Atomen substituiert ist und höchstens 3 Substituenten trägt, bedeuten.
Bevorzugt ist flammfest ausgerüstete regenerierte Cellulose, welche dadurch gekennzeichnet ist, dass diese eine flammfest machende Verbindung der Formel
EMI1.5
enthält, worin R"f einen Phenylrest, der gegebenenfalls durch 1 oder 2 Chloratome, einen Methyl oder Methoxyrest und/oder ein Bromatom in ortho- oder para-Stellung substituiert ist, und höchstens 2 Substituenten trägt, R"2 Chlor, -OCH3, -OC2H5, -OC3H7,
EMI1.6
oder -OR"5, R"3 Wasserstoff, R"4 eine der Bedeutungen von R" oder R"3 und R"4 zusammen mit dem Stickstoffatom einen Piperidino- oder Morpholinoring bilden, und R"5 eine der Bedeutungen von R"1 bedeuten.
Bevorzugt ist weiter flammfest ausgerüstete regenerierte Cellulose, welche dadurch gekennzeichnet ist, dass diese eine flammfest machende Verbindung der Formel
EMI1.7
enthält, R"'1 einen Phenylrest, der gegebenenfalls durch 1 oder 2 Chloratome oder einen Methylrest oder ein Bromatom in ortho- oder para-Stellung substituiert ist, R"'2 Chlor, -OC2H5,
EMI1.8
oder OR"'5, R"'3 Wasserstoff, R"'4 eine der Bedeutungen von R"'t oder R"'3 und R"'4 zusammen mit dem Stickstoffatom einen Piperidino- oder Morpholinorest bilden, und R"'5 eine der Bedeutungen von R"' bedeuten.
Bevorzugt ist auch flammfest ausgerüstete Cellulose, welche dadurch gekennzeichnet ist, dass diese eine flammfest machende Verbindung der Formel
EMI1.9
enthält, worin R"'1 die obige Bedeutung hat.
Die Erfindung betrifft auch ein Verfahren zur Herstellung von flammfest ausgerüsteter regenerierter Cellulose, welches dadurch gekennzeichnet ist, dass man diese aus einer Lösung ausfällt, die eine Verbindung der obigen Formel (1) enthält.
Unter regenerierter Cellulose sind die bekannten Derivate nativer Cellulose zu verstehen wie z. B. die in Form des Alkalixanthogenats oder mit Tetraminkupfer-(ll)hydroxid ge löste und anschliessend ausgefällte Cellulose.
Als Alkylreste kommen, insofern nichts anderes be stimmt ist, natürlich vorkommende oder synthetisierbare pri märe, sekundäre oder tertiäre, geradkettige oder verzweigte infrage:
Beispiele für solche primäre Reste sind Methyl, Äthyl,
Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Undecyl,
Dodecyl.
Beispiele für sekundäre Reste sind Isopropyl, 2-Butyl.
Beispiele für substituierte Phenylreste sind o-, m- oder p-Methylphenyl, 2-, 3- oder 4-Chlorphenyl, 3- oder 4-Bromphenyl, 2,3-, 2,4-, 2,5; 3,4- oder 3,5-Dichlorphenyl, 2,4,5-Trichlorphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-Dimethylphenyl, 2,4,5-, 2,4,6-Trimethylphenyl, 2-Methyl-4-bromphenyl, 3-Methyl-4-bromphenyl, 2-Chlor-6-methylphenyl, 3-Chlor-2-methylphenyl, 4-Chlor-2 methylphenyl, 5-Chlor-2-methylphenyl, 2-, 4-Athylphenyl, 2,4-Diäthylphenyl, p-, o-, m-Methoxyphenyl, 3-Chlor-4methoxy phenyl, 3-Chlor-6-methoxyphenyl, vorzugsweise Phenyl, 4-Chlorphenyl, 4-Bromphenyl, 3,4- und 2,5-Dichlorphenyl. Für den Rest -N(R3)R4 kommen für R4 die genannten Reste infrage, wobei R5 vorzugsweise Wasserstoff bedeutet.
Die Substitution des Phenylringes für R1 durch Brom ist vorzugsweise in para-Stellung. Für R5 kommen z. B. auch die Reste Tetrachlorphenyl, Pentachlorphenyl, Tetrabromphenyl oder Pentabromphenyl infrage.
Die Herstellung der Verbindungen der Formel (I) bzw.
(Ia), (Ib), (Ic) und (Id) ist bekannt und z. B. in Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band 12/II, Seiten 978-981 beschrieben.
Beispiele für Verbindungen der Formel (I) sind:
EMI2.1
EMI2.2
EMI3.1
EMI3.2
Beim erfindungsgemässen Verfahren wird zunächst Cellulose in an sich bekannter Weise in Lösung gebracht, z. B. in ein lösliches Derivat übergeführt, beispielsweise mit Tetraminkupfer-(II)hydroxid oder nach der Xanthogenat-Methode.
Der so hergestellten Celluloselösung setzt man die Verbindung der Formel (I) zu. Die Zugabe kann man kontinuierlich oder diskontinuierlich unmittelbar durch intensives Rühren der Celluloselösung vornehmen. Man kann aber auch die Verbindungen der Formel (I) zuerst in Wasser fein dispergieren und als wässrige Dispersion der Celluloselösung zugeben. In allen Fällen kann es vorteilhaft sein, übliche Dispersionsstabilisatoren und Dispergatoren zuzufügen.
Die technisch wichtigen Eigenschaften der ausgefällten Regeneratcellulose werden, abgesehen von der Flammwidrigkeit, durch die Zufügung der Reaktionsprodukte nur unwesentlich beeinflusst. Bezogen auf die a-Cellulose kann man beispielsweise 10 bis 35 Gewichtsprozent davon in der Celluloselösung verteilen. Bevorzugt verwendet man Mengen von
15-25 Gewichtsprozent. Aus der Celluloselösung, die diese Verbindungen enthält, wird in an sich bekannter Weise das Celluloseregenerat unter Formgebung ausgefällt. Als formgebende Massnahme kommt vor allem die Bildung von Fäden und Folien durch Einleiten der Celluloselösung in ein Fällbad, unter Verwendung von feinen Düsen oder Schlitzen, in Betracht. Man kann dabei die bei der Herstellung von Celluloseregeneratfäden oder -folien üblichen Fällbäder benützen.
Dabei werden die in der Celluloselösung enthaltenen, flammhemmenden Umsetzungsprodukte weitgehend in dem ausgefällten Celluloseregenerat-Material eingeschlossen.
In den folgenden Beispielen sind die Teile Gewichtsteile, die Prozente Gewichtsprozente, die Grade Celsiusgrade.
Herstellung der Verbindung der Formel
EMI3.3
In einem Rührgefäss werden 45,7 Teile Thiophosphorylchlorid (PSCl3), 235 Teile Xylol und 70 Teile Anilinhydrochlorid gemischt und unter leichtem Stickstoffstrom auf 1200 erwärmt. Man hält das Gemisch 15 Stunden bei dieser Temperatur und erwärmt anschliessend weitere 45 Stunden bei 135". Nach beendeter Reaktion kühlt man das Gemisch ab, filtriert den ausgeschiedenen Feststoff ab und trocknet. Das erhaltene Kristallpulver wird in verdünnter Salzsäure suspendiert, danach abfiltriert, mit Wasser neutral gewaschen. Man erhält etwa 50 Teile einer Verbindung der Formel (s), die durch Umkristallisation aus Chlorbenzol weiter gereinigt wird. Eine Umkristallisation ist jedoch zu der erfindungsgemässen Herstellung schwer entflammbarer, regenerierter Cellulose nicht erforderlich.
Das Produkt stellt einen weissen Feststoff vom Schmelzpunkt 243-246 dar. In analoger Weise stellt man z. B. die Verbindung der Formel (u) vom Smp. 238-240 "C dar, indem man z. B. von 67,8 Teilen Thiophosphorylchlorid, 610 Teilen Xylol und 131,2 Teilen p-Chloranilinhydrochlorid ausgeht.
Herstellung von flammfest ausgerüsteter regenerierter Cellulose Beispiel 1
In 200 Teile einer Celluloselösung auf Xanthogenat-Basis, welche 18 Teile n-Cellulose enthalten, werden 18 Teile einer 20% wässrigen Dispersion des flammwidrigen Wirkstoffes der Formel (s) eingerührt.
Eine solche Dispersion wird in folgender Art hergestellt:
15 Teile der Verbindung (s) werden mit 3,75 Teilen eines Dispergators auf der Basis von Natriumnaphthalinsulfonat und 56,25 Teilen Wasser in Gegenwart von 75 Teilen Quarzit perlen während 4 Stunden sandgemahlen, wobei man unter Kühlung mit Eis bei einer Tourenzahl von 1500 Umdrehun- gen pro Minute arbeitet. Nach Abtrennen der Quarzitperlen durch Filtration erhält man 67 Teile einer Dispersion, welche 20% Wirkstoff enthält. Die oben beschriebene, mit flammwidrigem Wirkstoff versehene Celluloselösung wird nach einem üblichen Spinnverfahren durch Düsen in ein Fällbad gepresst, welches pro Liter folgende Substanzen enthält:
125 g Schwefelsäure, 240 g Natriumsulfat (wasserfrei) und 12 g Zinksulfat (wasserfrei). Die erhaltene Faser wurde ausreichend nachgewaschen und zu Gewirken verarbeitet.
Die Gewirke wurden nach dem Verfahren von Fenimore und Martin (Vergleiche Modern Plastics, November 1966) durch Bestimmung des Sauerstoff-Grenzwertes (LOI-Wert) auf ihre Flammfestigkeit hin geprüft.
Beispiel 2
Man verfährt wie in Beispiel 1, verwendet jedoch den flammwidrigen Wirkstoff der Formel (u).
Man erhält wiederum ein Gewirke aus regenerierter Cellulose mit flammwidrigen Eigenschaften.
The present invention relates to regenerated cellulose with a flame-retardant finish, which is characterized in that it is a compound of the formula which makes it flame-resistant
EMI1.1
wherein R1 is an alkyl radical with 1-12 carbon atoms, cyclohexyl, a phenyl radical, optionally with 1-3 chlorine atoms, 1-3 alkyl or alkoxy radicals with a maximum of 6 carbon atoms, the individual alkyl or alkoxy radical at most 4 C. -Atoms and / or a bromine atom is substituted in the ortho or para position and has a maximum of 3 substituents, R2 is chlorine,
EMI1.2
or OR5, R3 hydrogen, methyl or ethyl, R4 one of the meanings of Rl, or R3 and R4 together, optionally via a further heteroatom, are linked to form a heterocyclic ring, and R5 is an alkyl radical with 1-12 C atoms, cyclohexyl, a phenyl radical,
which is optionally substituted by 1-5 chlorine atoms, 1-5 bromine atoms and / or 1-3 alkyl or alkoxy radicals with a total of at most 9 carbon atoms, the individual alkyl or alkoxy radical having at most 9 carbon atoms.
Flame-resistant regenerated cellulose is preferred, which is characterized in that it is a flame-resistant compound of the formula
EMI1.3
contains, wherein R'1 is a methyl radical, cyclohexyl, a phenyl radical, which is optionally replaced by 1 or 2 chlorine atoms, an Al.
alkyl or alkoxy radical with 1-4 carbon atoms and / or one bromine atom is substituted in the ortho or para position and has a maximum of 2 substituents, R'2 is chlorine,
EMI1.4
or -OR'5, R'3 hydrogen, methyl or ethyl, R'4 one of the meanings of R'l, or R'3 and R'4 together with the nitrogen atom form a piperidino, morpholino or pyrrolidino ring, and R '5 is an alkyl radical with 1-6 carbon atoms, cyclohexyl, a phenyl radical which is optionally substituted by 1-3 chlorine atoms, 1-3 bromine atoms and / or an alkyl or alkoxy radical with 1-4 carbon atoms and a maximum of 3 substituents wears, mean.
Flame-resistant regenerated cellulose is preferred, which is characterized in that it is a flame-resistant compound of the formula
EMI1.5
contains, where R "f is a phenyl radical which is optionally substituted by 1 or 2 chlorine atoms, a methyl or methoxy radical and / or a bromine atom in the ortho or para position, and has at most 2 substituents, R" has 2 chlorine, -OCH3, -OC2H5, -OC3H7,
EMI1.6
or -OR "5, R" 3 is hydrogen, R "4 has one of the meanings of R" or R "3 and R" 4 together with the nitrogen atom form a piperidino or morpholino ring, and R "5 has one of the meanings of R" 1 mean.
Also preferred is regenerated cellulose with a flame-proof finish, which is characterized in that it is a flame-proofing compound of the formula
EMI1.7
contains, R "'1 a phenyl radical which is optionally substituted by 1 or 2 chlorine atoms or a methyl radical or a bromine atom in the ortho or para position, R"' 2 chlorine, -OC2H5,
EMI1.8
or OR "'5, R"' 3 hydrogen, R "'4 one of the meanings of R"' t or R "'3 and R"' 4 together with the nitrogen atom form a piperidino or morpholino radical, and R "'5 mean one of the meanings of R "'.
Flame-resistant cellulose is also preferred, which is characterized in that it is a flame-resistant compound of the formula
EMI1.9
contains, wherein R "'1 has the above meaning.
The invention also relates to a method for producing regenerated cellulose with a flame-resistant finish, which is characterized in that it is precipitated from a solution which contains a compound of the above formula (1).
Under regenerated cellulose, the known derivatives of native cellulose are to be understood such. B. in the form of the alkali metal oxanthate or with tetramine copper (II) hydroxide dissolved and then precipitated cellulose.
Unless otherwise specified, the alkyl radicals are naturally occurring or synthesizable primary, secondary or tertiary, straight-chain or branched ones:
Examples of such primary radicals are methyl, ethyl,
Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl,
Dodecyl.
Examples of secondary radicals are isopropyl and 2-butyl.
Examples of substituted phenyl radicals are o-, m- or p-methylphenyl, 2-, 3- or 4-chlorophenyl, 3- or 4-bromophenyl, 2,3-, 2,4-, 2,5; 3,4- or 3,5-dichlorophenyl, 2,4,5-trichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-dimethylphenyl, 2,4,5-, 2,4,6-trimethylphenyl, 2-methyl-4-bromophenyl, 3-methyl-4-bromophenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 4-chloro -2 methylphenyl, 5-chloro-2-methylphenyl, 2-, 4-ethylphenyl, 2,4-diethylphenyl, p-, o-, m-methoxyphenyl, 3-chloro-4methoxy phenyl, 3-chloro-6-methoxyphenyl, preferably phenyl, 4-chlorophenyl, 4-bromophenyl, 3,4- and 2,5-dichlorophenyl. For the radical —N (R3) R4, the radicals mentioned are suitable for R4, where R5 is preferably hydrogen.
The substitution of the phenyl ring for R1 by bromine is preferably in the para position. For R5 z. B. also the radicals tetrachlorophenyl, pentachlorophenyl, tetrabromophenyl or pentabromophenyl in question.
The preparation of the compounds of the formula (I) or
(Ia), (Ib), (Ic) and (Id) are known and e.g. B. in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 12 / II, pages 978-981.
Examples of compounds of the formula (I) are:
EMI2.1
EMI2.2
EMI3.1
EMI3.2
In the process according to the invention, cellulose is first brought into solution in a manner known per se, e.g. B. converted into a soluble derivative, for example with tetramine copper (II) hydroxide or by the xanthate method.
The compound of the formula (I) is added to the cellulose solution thus prepared. The addition can be carried out continuously or discontinuously directly by vigorous stirring of the cellulose solution. However, the compounds of the formula (I) can also be finely dispersed in water first and added to the cellulose solution as an aqueous dispersion. In all cases it can be advantageous to add customary dispersion stabilizers and dispersants.
The technically important properties of the precipitated regenerated cellulose are, apart from the flame retardancy, only insignificantly influenced by the addition of the reaction products. Based on the α-cellulose, for example 10 to 35 percent by weight thereof can be distributed in the cellulose solution. Preference is given to using amounts of
15-25 percent by weight. From the cellulose solution containing these compounds, the regenerated cellulose is precipitated in a manner known per se while being shaped. The formation of threads and foils by introducing the cellulose solution into a precipitation bath using fine nozzles or slits is particularly suitable as a shaping measure. One can use the precipitation baths customary in the production of regenerated cellulose threads or films.
The flame-retardant reaction products contained in the cellulose solution are largely enclosed in the precipitated regenerated cellulose material.
In the following examples, parts are parts by weight, percentages are percentages by weight, degrees Celsius.
Preparation of the compound of formula
EMI3.3
45.7 parts of thiophosphoryl chloride (PSCl3), 235 parts of xylene and 70 parts of aniline hydrochloride are mixed in a stirred vessel and heated to 1200 under a gentle stream of nitrogen. The mixture is kept at this temperature for 15 hours and then heated for a further 45 hours at 135 ". After the reaction has ended, the mixture is cooled, the precipitated solid is filtered off and dried. The crystal powder obtained is suspended in dilute hydrochloric acid, then filtered off with water About 50 parts of a compound of the formula (s) are obtained, which are further purified by recrystallization from chlorobenzene, however, recrystallization is not necessary for the inventive production of flame-retardant, regenerated cellulose.
The product is a white solid with a melting point of 243-246. In an analogous manner, z. B. the compound of the formula (u) with a melting point of 238-240 "C, by starting, for example, with 67.8 parts of thiophosphoryl chloride, 610 parts of xylene and 131.2 parts of p-chloroaniline hydrochloride.
Production of regenerated cellulose with a flame-proof finish Example 1
18 parts of a 20% aqueous dispersion of the flame-retardant active ingredient of the formula (s) are stirred into 200 parts of a xanthate-based cellulose solution which contains 18 parts of n-cellulose.
Such a dispersion is made in the following way:
15 parts of the compound (s) are sand-milled with 3.75 parts of a dispersant based on sodium naphthalene sulfonate and 56.25 parts of water in the presence of 75 parts of quartzite beads for 4 hours, while cooling with ice at a speed of 1500 revs - works per minute. After the quartzite beads have been separated off by filtration, 67 parts of a dispersion are obtained which contain 20% of active ingredient. The cellulose solution described above, provided with a flame-retardant active ingredient, is pressed using a conventional spinning process through nozzles into a precipitation bath, which contains the following substances per liter:
125 g sulfuric acid, 240 g sodium sulfate (anhydrous) and 12 g zinc sulfate (anhydrous). The fiber obtained was sufficiently rewashed and made into knitted fabrics.
The knitted fabrics were tested for flame resistance by the method of Fenimore and Martin (compare Modern Plastics, November 1966) by determining the oxygen limit value (LOI value).
Example 2
The procedure is as in Example 1, but using the flame-retardant active ingredient of the formula (u).
A knitted fabric made of regenerated cellulose with flame-retardant properties is again obtained.
Claims (1)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH193474A CH575476A5 (en) | 1974-02-12 | 1974-02-12 | Flameproof regenerated cellulose - contg. substituted cyclo-diphosphazans as flame inhibitors |
| SE7413723A SE7413723L (en) | 1973-11-09 | 1974-10-31 | |
| DE19742451802 DE2451802A1 (en) | 1973-11-09 | 1974-10-31 | FLAME RESISTANT REGENERATED CELLULOSE |
| FI3203/74A FI320374A (en) | 1973-11-09 | 1974-11-01 | |
| NO743938A NO743938L (en) | 1973-11-09 | 1974-11-01 | |
| NL7414396A NL7414396A (en) | 1973-11-09 | 1974-11-05 | Flameproof regenerated cellulose - contg. substituted cyclo-diphosphazans as flame inhibitors |
| JP49127637A JPS5079560A (en) | 1973-11-09 | 1974-11-07 | |
| GB48291/74A GB1487937A (en) | 1973-11-09 | 1974-11-07 | Regenerated cellulose flameproofed by phosphorus-nitrogen heterocyclic compounds |
| IT53933/74A IT1023116B (en) | 1973-11-09 | 1974-11-08 | REGENERATED CELLULOSE DIFFICULTY FLAMMABLE PROCEDURE FOR OBTAINING IT AND INDUSTRIAL PRODUCTS THAT CONTAIN IT |
| FR7437050A FR2250813B1 (en) | 1973-11-09 | 1974-11-08 | |
| ES431765A ES431765A1 (en) | 1973-11-09 | 1974-11-08 | Regenerated cellulose flameproofed by phosphorus-nitrogen heterocyclic compounds |
| US05/951,393 US4210451A (en) | 1973-11-09 | 1978-10-16 | Regenerated cellulose flameproofed with organophosphorylamides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH193474A CH575476A5 (en) | 1974-02-12 | 1974-02-12 | Flameproof regenerated cellulose - contg. substituted cyclo-diphosphazans as flame inhibitors |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH575476A5 true CH575476A5 (en) | 1976-05-14 |
Family
ID=4222003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH193474A CH575476A5 (en) | 1973-11-09 | 1974-02-12 | Flameproof regenerated cellulose - contg. substituted cyclo-diphosphazans as flame inhibitors |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH575476A5 (en) |
-
1974
- 1974-02-12 CH CH193474A patent/CH575476A5/en not_active IP Right Cessation
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