GB1598744A - Flame-proofed cellulose acetate - Google Patents

Flame-proofed cellulose acetate Download PDF

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GB1598744A
GB1598744A GB15154/78A GB1515478A GB1598744A GB 1598744 A GB1598744 A GB 1598744A GB 15154/78 A GB15154/78 A GB 15154/78A GB 1515478 A GB1515478 A GB 1515478A GB 1598744 A GB1598744 A GB 1598744A
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cellulose acetate
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    • 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
    • C07F9/6571—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 oxygen atoms as the only ring hetero atoms
    • C07F9/657109—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 oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • 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

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Description

(54) FLAME-PROOFED CELLULOSE ACETATE (71) We, SANDOZ LTD., of 35 Lichtstrasse, 4002 Basle, Switzerland, a Swiss Body Corporate, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to flameproofed cellulose acetate and its method of production.
According to the present invention there is provided flameproofed cellulose acetate including, as a flameproofing agent not more than 5% (by weight of cellulose acetate) of one or more compounds of formula I,
in which each R, independently, is a radical -OR1 (a) or
Y is oxygen or sulphur, Q is a radical 4 (c)
wherein each R, independently, and Y, independently, are as defined above, each R1, independently, is methyl; ethyl or propenyl, each unsubstituted or substituted with up to 3 halogen atoms or with a (C,~6)alkoxy radical; (C3~,2)alkyl or (C4-12)alkenyl, each unsubstituted or substituted with up to 4 halogen atoms; (C5-8)cycloalkyl or (C5-8)cycloalkyl-(C1-4)alkyl, containing 7-9 carbon atoms in toto, each unsubstituted or ringsubstituted with 1 or 2 halogen atoms; or phenyl or phenyl-(C1-4)alkyl, each unsubstituted or aromatically substituted with up to 5 halogen atoms, with up to 3 (C1-3)alkyl radicals, or with up to 3 (C1-3)alkoxy radicals, or two moieties R1 bound via oxygen atoms to the same phosphorous atom form a radical (f).
and each of the other two moieties R1, when present, independently, is a radical as defined above or the other two moieties R1, when present together form a second radical (f), independent from the first radical (f), either the or each R2, independently, is C(1-4)alkyl, cyclohexyl or benzyl; or phenyl, unsubstituted or substituted with 1 or 2 chlorine atoms of which at most one can occupy an ortho-position, or with a bromine atom in the para-position, or with up to 2 (C1~3)alkyl or up to 2 (C1~3)alkoxy radicals, the aggregate of the carbon atoms thereof not exceeding 3, and the or each R3, independently, is (C1 4)alkyl or hydrogen, or any R2 and R3, independently from any other R2 and R3, together with the nitrogen atom to which they are bound, form a 5- or 6-membered, saturated heterocyclic ring which may optionally contain as a ring member an oxygen or sulphur atom, or a second nitrogen atom to which is bound a (C14)alkyl radical, R4 is (C2-18)alkyl, unsubstituted or substituted with up to 3 halogen atoms or with a (C1-6)alkoxy radical; (C3-10)alkenyl, unsubstituted or substituted with up to 3 halogen atoms; cyclohexyl; benzyl; or phenyl, unsubstituted or substituted with up to 5 substituents selected from chlorine and bromine atoms and methyl and ethyl groups, R5 is ethylene; straight or branched chain (C310)alkylene or straight or branched chain (C410)alkenylene, each having at least two bridging carbon atoms and being unsubstituted or substituted with I or 2 halogen atoms; straight chain (C410alkynylene; or a divalent radical selected from those of formulae
Z, or each Z, is oxygen or sulphur, n is zero or 1, A is a radical (a), as defined above, or a radical
X is oxygen or sulphur, either each R6 and R7, independently, is hydrogen, (C14)alkyl, -CH2C!, -CH2Br or phenyl not more than one being phenyl, or any R6 and R7 together with the carbon atom to which they are bound, independently from any other CR6R7 moiety, form a cyclohexylidene, cyclohexenylidene or 3,4-dibromocyclohexylidene ring, each R8 and R10, independently, is hydrogen or (C1-4)alkyl, each R9, independently, is hydrogen or methyl, each of m, m1 and m2 is zero, 1, 2, 3 or 4 the sum of m1 and m2 not exceeding 4, each of n1 and n2, independently, is an integer from 1 to 6, X1 is oxygen or sulphur, either R11 is methyl; ethyl, unsubstituted or substituted with a halogen atom; propyl, unsubstituted or substituted with 1 or 2 halogen atoms; (C412)alkyl, unsubstituted or substituted with up to 3 halogen atoms; cyclohexyl; benzyl; or phenyl, unsubstituted or substituted with 1 or 2 chlorine atoms, or with a bromine atom in the para-position and/or in both cases with up to 2 (C1~3)alkyl and/or (C1~3)alkoxy radicals, the aggregate of the carbon atoms thereof not exceeding 3, and R12 is hydrogen; methyl; ethyl, unsubstituted or substituted with a halogen atom; propyl, unsubstituted with up to 2 halogen atoms; (C412)alkyl, unsubstituted or substituted with up to 3 halogen atoms; cyclohexyl; benzyl; or phenyl, or R11 and R12, together with the nitrogen atom to which they are bound, form a 5- or 6-membered, saturated heterocyclic ring which may contain as a ring member an oxygen or sulphur atom, or a second nitrogen atom to which is bound a (C1~4)alkyl radical, with the provisos: (i) when Q is a radical (c) or (d), then neither R can be a radical (b), (ii) when Q is a radical (c) and R4 signifies (C218)alkyl substituted with (C1-6)alkoxy, then such alkoxy substitutent cannot be on the α-position of the alkyl radical, (iii) when Q is a radical (c), then the OR1,s signified by the two R's can only form together a radical
(iv) when Q is a radical (d), R5 signifies optionally halogen-substituted, branched chain C5 alkylene and both pairs of OR1,s, independently, signify radicals
then R5 can only signify branched chain C5 alkylene substituted with at least one halogen atom, (v) when Q is a radical (e), and at least one of the Y's and X is oxygen, then Z can only be oxygen, (vi) when two radicals (b) are attached to a phosphorus atom and Y attached to that same phosphorus atom is sulphur, then both the moieties R2 in these radicals (b) are (C14)alkyl, (vii) when n is 1, or when n is zero and R2 in any radical (b) is (C14alkyl, then each R3 present, or R3 in that same radical (b), respectively, can only be (C14)alkyl, (viii) at least one of R6, R7, R8, R9 and R10 in any radical (f) is other than hydrogen, and (ix) when each of R6 and R, independently, in any radical (f) is -CH2Cl or -CH2Br, or both R6 and R,, together with the carbon atom to which they are bound form a cyclohexylidene, cyclohexenylidene or 3,4 dibromocyclohexylidene ring, then each of Ra, R9 and R10 in the same radical (f) is hydrogen.
In the above definition of formula I, it is to be understood that the term "halogen" means chlorine or bromine.
When any R1 is unsubstituted or substituted alkyl, the alkyl radical preferably contains 1 to 6, more preferably 3 to 6, even more preferably 3 or 4, and most preferably 3 carbon atoms. When any R1 is substituted ethyl, the substituent is preferably a single chlorine or bromine atom, and when a substituted (C312)alkyl radical, this is preferably substituted with up to 3 chlorine or up to 3 bromine atoms. In the case of R1 being substituted n-propyl or isopropyl, this preferably bears 1 or 2 chlorine or I or 2 bromine atoms. Preferably, however, any alkyl radical signified by R1 is unsubstituted. If Q is a radical (e) and there are more than 2 R, moieties present, preferably no more than 2 of these signify ethyl.
When any R, is unsubstituted or substituted alkenyl, the alkenyl radical preferably contains 3 to 6 carbon atoms, which when substituted, preferably bears 1 or 2 chlorine or 1 or 2 bromine atoms.
When any R1 is unsubstituted or substituted cycloalkyl, this is preferably unsubstituted cyclohexyl.
When any R1 is substituted phenyl, the substituents are preferably up to 3 halogen atoms or up to 3 methyl groups, more preferably, in the case where Q is a radical (c) or (d), up to 3 chlorine atoms or a bromine atom in the para-position, or, in the case where Q is a radical (e), up to 3 chlorine atoms, or a bromine atom in the para position, or up to 3 methyl groups, more preferably a single methyl group.
When any R1 is unsubstituted or substituted phenyl, this is preferably unsubstituted phenyl in the case where Q is a radical (c) or (d) and unsubstituted or mono-methyl substituted phenyl in the case where Q is a radical (e).
When any R1 is substituted phenylalkyl, this is preferably phenylalkyl substituted with up to 3 chlorine atoms, or a bromine atom in the para-position, or up to 3 methyl groups. In this case where Q is a radical (c) or (d), any optionally substituted phenylalkyl radical signified by R1 is preferably unsubstituted. In all cases, the radical is preferably optionally substituted benzyl, more preferably unsubstituted benzyl.
When any R6 or R7 is alkyl, this is preferably (C13)alkyl, more preferably methyl, and when any R6 and R7 together with the carbon atom to which they are bound form a ring, this is preferably a 3,4-dibromocyclohexylidene ring. If R6 is -CH2Cl, R7 bound to the same carbon atom is preferably other than KH2Br, and vice versa. H2Br is preferred to H2Cl. Preferably at least one of R6 and R7 in any radical (f) is other than hydrogen, and more preferably either each of R6 and R7, independently, is alkyl, -CH2Cl or -CM2Br, or R6 and R7 together with the carbon atom to which they are bound form a ring. Even more preferably, each of R6 and R7, independently, in any radical (f) is alkyl, -CH2Cl or -CH2Br, most preferably alkyl. It is also preferred that R6 and R7 in any radical (f) have the same meaning.
When any R8 or R10 is alkyl, this is preferably methyl. Each of R8, R9 or Rlos independently, in any radical (f) is preferably hydrogen.
In the case where Q is a radical (d), it is in general preferred that either any R is optionally substituted alkyl, cycloalkyl, phenyl or phenylalkyl, or two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f). More preferably, either any R1 is optionally substituted alkyl, cycloalkyl or phenyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f). Most preferably, either any R1 is optionally substituted alkyl or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f), of which the latter significance is preferred to the former.
In the case where Q is a radical (e), it is in general preferred that either any R1 is optionally substituted alkyl, alkenyl, cycloalkyl, phenyl or phenylalkyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f). Depending on the significances of the two moieties Y, Z and n, any R1 has certain more preferred significances. Thus when the two moieties Y are both sulphur, Z is oxygen and n is zero, preferably either any R, is optionally substituted alkyl, cycloalkyl or phenyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f), and more preferably any R1 is optionally substituted alkyl, especially n-propyl or isopropyl, optionally substituted with up to 2 chlorine or up to 2 bromine atoms, or unsubstituted (C46)alkyl. When the two moieties Y and Z are all sulphur and n is zero, preferably either any R1 is optionally substituted alkyl, especially unsubstituted propyl or butyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f), of which the latter significance is preferred to the former. Finally, when the two moieties Y are both sulphur, Z is oxygen, n is 1 and A is a radical (g), preferably either any R1 is optionally substituted alkyl, especially n-propyl or isopropyl, optionally substituted with up to 2 chlorine or up to 2 bromine atoms or unsubstituted (C4~6)alkyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f), of which the latter significance is preferred to the former.
In general, whenever Q is a radical (e) and more than two moieties R1 are present, preferably no more than two of these are ethyl.
When any R2 is alkyl, this is preferably (C1~3)alkyl, and when it is substituted phenyl, the phenyl radical is preferably substituted with a single chlorine or bromine atom or alkyl group, the latter preferably being methyl, more preferably substituted with a single chlorine atom in the para-position or with a methyl group, and most preferably substituted with a methyl group, especially in the orthoposition.
In general, any R2 is preferably alkyl or optionally substituted phenyl, of which the optionally substituted phenyl is preferably unsubstituted, and more preferably optionally substituted phenyl.
When any R3 is alkyl, this is preferably (C;~3)alkyl. In general, however, R, is preferably hydrogen.
Furthermore, when either of R2 and R3 is ethyl or propyl, the other is preferably also ethyl or propyl, respectively.
When R4 is unsubstituted or substituted alkyl, the alkyl radical preferably contains 2 to 6 carbon atoms, and more preferably 2 to 5 carbon atoms. The substituents are preferably I or 2 halogen atoms or an alkoxy radical. Any halogen or alkoxy substituent is preferably bromine or methoxy, respectively.
When R4 is unsubstituted or substituted alkenyl, this preferably contains 3 to 6 carbon atoms, and more preferably 3. The substituents are preferably 2 bromine atoms. The most preferred meaning is 2,3-dibromopropen-2-yl.
When R4 is substituted phenyl, the preferred substituents are up to 3 chlorine atoms, up to 3 bromine atoms, or up to 3 methyl groups.
In general, R4 is preferably optionally substituted alkenyl or phenyl.
When R5 is unsubstituted or substituted alkylene, this preferably contains up to 6, more preferably up to 5, carbon atoms. The substituents are preferably 1 or 2 chlorine atoms or 1 or 2 bromine atoms. Except in the case where R5 is unsubstituted or substituted C5 alkylene, the alkylene is preferably straight chain.
In the case of optionally substituted C5 alkylene, this is preferably 2,2dihalomethyltrimethylene.
When R5 is unsubstituted or substituted alkenylene, this preferably contains 4 carbon atoms, is straight chain, and when substituted bears 2 chlorine or 2 bromine atoms. Most preferably it is one of the groups --CH,CH=CHCH,,-, --CH,C(CI)=C(CI)CH, and -CH2C(Br)=C(Br)C112-.
When R5 is alkynylene, this preferably contains 4 carbon atoms, and more particularly, is -CM2C=-CCM2-.
Of the significances optionally bromine-substituted o- or p-phenylene signified by R5, the optionally bromine-substituted p-phenylene is preferred.
When R5 is a radical of formula
each of n1 and n2, independently is preferably 1 or 2, and when R5 is a radical of formula
A1 ls preferably oxygen.
In general, R5 is preferably unsubstituted or substituted alkylene or alkenylene, alkynylene, or one of the divalent radicals
and most preferably unsubstituted or substituted alkylene or alkenylene, alkynylene, or the divalent radical
When R11 or R12 is unsubstituted or substituted alkyl, this preferably contains up to 4 carbon atoms, and independently, is preferably unsubstituted. When R11 is unsubstituted or substituted phenyl, this is preferably unsubstituted.
The preferred heterocyclic radicals formed by R", R12 and the nitrogen atom to which they are bound are piperidino and morpholino, of which piperidino is more preferred.
On the same radical (g), R11 and R,2 preferably have the same significance.
Of all the significances of R,1, the preferred ones are unsubstituted or substituted alkyl, cyclohexyl and benzyl, and, together with R12 and the nitrogen atoms to which both are bound, a 5- or 6-membered saturated heterocyclic ring.
For R12 the preferred significances are hydrogen, unsubstituted or substituted alkyl and, together with R11 and the nitrogen atom to which both are bound, a 5- or 6 membered saturated heterocyclic ring. More preferably, either of R11 and R12, independently, is unsubstituted or substituted alkyl or both, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring.
A is preferably a radical (g), n is preferably zero, and X is preferably sulphur, each independently.
When Q is a radical (c) or (d), Y is preferably sulphur, and, independently, the compounds in which Q is a radical (d) are preferably symmetrical, i.e. the two pairs of terminal moieties R, form identical radicals (f), or the four moieties R, individually have identical significances.
When Q is a radical (e), the two moieties Y and Z are all oxygen and n is zero, each R, independently, is preferably a radical (b). When Q is a radical (e), and either the two moieties Y are both sulphur, Z is oxygen and n is zero or I, or the two moieties Y and Z all sulphur and n is zero, each R, independently, is preferably a radical (a).
For the compounds of formula I in which Q is a radical (d) or (e), both moieties Y preferably have the same significance.
Of all the compounds of formula I, those in which Q is a radical (e) and n is zero are the most preferred.
Particular classes of compounds within the scope of the compounds of formula I, as defined above, useful as flameproofing agents for flameproofed cellulose acetate according to the present invention are the compounds of formulae la, Jb ~~~ and Ic:
in which R4, R6, R7, R8, R9, R10 and Y are as defined above and the provisos (ii), (viii) and (ix) apply.
in which each R1, independently, and/or the or both radicals (f) formed by the or both sets of two moieties R1 bound via oxygen atoms to the same phosphorus atom, R5 and Y are as defined above, and the provisos (iv), (viii) and (ix) apply.
in which each R, indpendently, Z or each Z, n, A, X and Y are as defined above and the provisos (v), (vi), (vii), (viii) and (ix) apply: The flameproofed cellulose acetate of the present invention preferably includes, as a flameproofing agent, one or more compounds of formula I' or I",
in which Q' is a radical -OR4, (c') or
each R1, independently, is ethyl; chloroethyl; bromoethyl; (C312)alkyl, unsubstituted or substituted with up to 3 chlorine atoms or up to 3 bromine atoms; cyclohexykl; phenyl, unsubstituted or substituted with up to 3 halogen atoms or up to 3 methyl groups; or benzyl, or two moieties R1' bound via oxygen atoms to the same phosphorous atom form a radical (f'),
and each of the other two moieties R;, when present, independently, is a radical as defined above, or the other two moieties R11, when present, together form a second radical (f'), independent from the first radical (f'), R4 is (C26)alky1, unsubstituted or substituted with up to 3 halogen atoms or a methoxy group: 2,3-dibromopropen-2-yl; cyclohexyl; benzyl: or phenyl, unsubstituted or substituted with up to 5 substituents selected from chlorine and bromine atoms and methyl and ethyl groups, R5, is ethylene; straight or branched chain (C3 6)alkylene, having at least 2 bridging carbon atoms and being unsubstituted or substituted with 1 or 2 chlorine atoms or 1 or 2 bromine atoms: or a divalent radical selected from those of formulae -CH2CH=CHCH2- -CH2C(Cl)=C(Cl)CH2 -CH2C(Br)=C(Br)CH2- -CH2C#CCH2-
each R6 and R;, independently, is (C14)alkyl, -CH2Cl or -CH2Br, or any R6' and R7' together with the carbon atom to which they are bound, independently from any other > CR6'R7', moiety, form a cyclohexylidene, cyclohexenylidene or 3,4-dibromocyclohexylidene ring, and m is zero, 1, 2, 3 or 4, with the provisos: (i) when Q' is a radical (c') abd R4' signifies (C2-6)alkyl substituted with a methoxy group then such methoxy substitutent cannot be on the α- position of the alkyl radical, (ii) when Q' is a radical (c'), then the OR1's can only form together a radical (f'), and (iii) when Q' is a radical (d'), R5' signifies optionally hallogen-substituted, branched chain C5 alkylene and both pairs of OR1' s, independently, signify radicals
then R5' can only signify branched chain C5-akylene with at least one halogen atom
in which each R", independently, is a radical -OR"1 (a') or Y is oxygen or sulphur,
each R"1, independently, is ethyl; chloroethyl; bromoethyl: (C3 6)alkyl. unsubstituted or substituted with up to 3 chlorine atoms or up to 3 bromine atoms; (C36)a1kenyl, unsubstituted or substituted with 1 or 2 chlorine atoms or 1 or 2 bromine atoms; cyclohexyl; phenyl, unsubstituted or substituted with up to 3 chlorine atoms, with a bromine atom in the para-position, or with up to 3 methyl groups; or benzyl, unsubstituted or aromatically substituted with up to 3 chlorine atoms or with a bromine atom in the para-position, or two moieties R"1 bound via oxygen atoms to the same phosphorus atom form a radical (f"),
and each of the other two moieties R"1 when present, independently, is a radical as defined above or the other two moieties R"1, when present, together form a second radical (f"), independent from the first radical (f"), the or each R'2, independently, is (C1~3)alkyl; or phenyl, unsubstituted or substituted with a chlorine atom, with a bromine atom in the para position, or with a methyl group, the or each R'3, independently, is (C1~3)alkyl or hydrogen, Z, or each Z, is oxygen or sulphur, n is zero or I X is oxygen or sulphur, either R'11 is (C14)alkyl, cyclohexyl, benzyl or phenyl, and R'12 is hydrogen, (C14)alkyl, cyclohexyl, benzyl or phenyl, or R'11 and R'12, together with the nitrogen atom to which they are bound, form a piperidino or morpholino ring, either each R'6 and each R'7, independently, is (C14)alkyl, -CH2Cl or -CH2Br, or any R6' and R7', together with the carbon atom to which they are bound, independently from any other > CR6'R7' moiety, form a cyclohexylidene, cyclohexenylidene or 3,4-dibromocyclohexylidene ring, with the provisos: (i) when at least one of the two Y's and Xis oxygen, then Z can only be oxygen, (ii) when two radicals (b') are attached to a phosphorus atom and Y attached to that same phosphorus atom is sulphur, then both the moieties R2 in those radicals (b') are (C1~3) alkyl, (iii) only when one of the moieties R'2 and R'3 bound to the same nitrogen - atom in a radical (b') is ethyl or propyl, can the other be ethyl or propyl, and (iv) when n is 1, or when n is zero and R'2 in any radical (b') is (C1-3)alkyl, then each of R'3 present, or R'3 in that same radical (b'), respectively, can only be (C1 3)alkyl.
The flameproofed cellulose acetate of the present invention most preferably includes, as a flameproofing agent, one or more compounds selected from those of formulae I'a, I'b, I'c, I"a, I"b, I"c and I"d following:
in which R'4a is 2,3-dibromopropen-2-yl; or phenyl, unsubstituted or substituted with up to 3 chlorine atoms, up to 3 bromine atoms or up to 3 methyl groups and each of R6a' and R7a', independently, is (C1-3)alkyl, -CH2Cl or -CH2Br, with the proviso that when one of R6a' and R7a' is -CH2Br, then the other is other than -CH2Cl.
in which each R1b' is n- or isopropyl, unsubstituted or substituted with 1 or 2 chlorine atoms or 1 or 2 bromine atoms, (C4-6)alkyl, unsubstituted or substituted with up to 3 chlorine atoms or with up to 3 bromine atoms: cyclohexyl; or phenyl, and R5b' is straight chain (C3-5)alkylene, unsubstituted or substituted with 1 or 2 chlorine atoms or 1 or 2 bromine atoms; or a divalent radical selected from those of formulae
in which R'sb, R'6a and R7a are as defined above.
in which RM2a is phenyl, unsubstituted or substituted with a chlorine atom in the para-position or with a methyl group.
in which each R"lb, independently, is n- or isopropyl, unsubstituted or substituted with 1 or 2 chlorine atoms or with 1 or 2 bromine atoms; (C4 6)alkyl unsubstituted or substituted with up to 3 chlorine atoms or with up to 3 bromine atoms; cyclohexyl; or phenyl, unsubstituted or substituted with a methyl group, or two moieties R1b" bound via oxygen atoms to the same phosphorus atom form a radical (f"')
and each of the other two moieties R1b" independently, is a radical as defined above or the other two moieties together form a second radical (fl") independent from the first radical (f"'), and each R"ab and R"7b, independently, is (C13)alkyl, -CH2Cl or -CH2Br, or any R6b" and R7b", together with the carbon atom to which they are bound, independently from any other > CR6b"R7b" moiety, form a 3,4 dibromocyclohexylidene ring, with the proviso that when one of R6b" and R"7b in any radical (f,") is -CH2Br, then the other is other than -CH2Cl.
in which each R"r, is propyl or butyl, or each of the two sets of two moieties RE1C bound via oxygen atoms to the same phosphorus atom form a radical (f"'), as defined above.
in which R',ld is n- or iso-propyl, unsubstituted or substituted with 1 or 2 chlorine atoms or with 1 or 2 bromine atoms; or (C46)alkyl, or each of the two sets of two moieties R"ld bound via oxygen atoms to the same phosphorus atom form a radical (f"'), as defined above, X is oxygen or sulphur, and either R"11 is (C14)alkyl, cyclohexyl or benzyl and R12 is hydrogen or (C1 4)alkyl, or R"11 and R"12, together with the nitrogen atom to which they are bound, form a piperidino or morpholino ring.
Of the compounds of formulae I'a, I'b, and I'c, those of formulae I'a and I'c are preferred as flameproofing agents in the flameproofed cellulose acetate of the present invention. Of the compounds of formulae I"a, I"b, I"c and I"d, those of formulae I"a, I"b and I"c are preferred as flameproofing agents in the flameproofed cellulose acetate of the present invention. In general, for the compounds of formula I in which Q is a radical (e), the halogen-free compounds are preferred.
The compounds of formula I are either known, or can be produced by known methods from available starting materials.
The present invention further provides a method of producing flameproofed cellulose acetate comprising incorporating the cellulose acetate not more than 5% by weight of cellulose acetate of one or more compounds of formula I, as defined above, as the flameproofing agent. A particularly preferred solvents employed are those conventionally used for the method comprising removal of the solvent from a cellulose acetate solution. In the case of cellulose 22 acetate and cellulose triacetate the preferred solvents are acetone and methylene chloride, respectively.
Hitherto, the amount of flameproofing agent usually incorporated in cellulose acetate for imparting satisfactory flameproofing properties thereto has been from 5 to 30 /O of the weight of the cellulose acetate substrate, more particularly 8 to 25 ,.
Surprisingly, however, effective flameproofing properties are realised in the cellulose acetate of the present invention with a content of flameproofing agent of not more than 5%. It is preferred to use an amount of at least 0.1 ,Ó. The more preferred range is however 0.5 to 5%, and most preferably 0.5 to 2%.
In the preferred method of the present invention as indicated above, the cellulose acetate can be dissolved in the solvent, e.g. acetone or methylene chloride, which already contains one or more compounds of formula I dissolved therein. Alternatively, the cellulose acetate is first dissolved in the solvent, and then the compound(s) of formula I is (are) dissolved or finely distributed in the resulting cellulose acetate solution, preferably with stirring. Thereafter the cellulose acetate is freed of the solvent by conventional methods e.g. by evaporation of the solvent with simultaneously shaping of the cellulose acetate.
Examples of the shaped forms of cellulose acetate are fibres, sheets and films.
Fibres and sheets may be produced by forcing the cellulose acetate solution through fine jets and slits, respectively, during which the solvent evaporates, and films may be produced by pouring the cellulose acetate solution onto a flat surface, e.g. glass, and allowing the solvent to evaporate. By such means the flameproofing agent is incorporated in the body of the cellulose acetate on being freed of the solvent.
The compounds of formula I can be employed as flameproofing agents for cellulose acetate in the presence of further monomeric or polymeric compounds, which contain aliphatically- or aromatically-bound halogen and also have flameproofing properties. Suitable such compounds include bis-(2,3dibromopropyl)terephthalate, 2,2-bis-[4-(2',3'-dibromopropoxy) - 3,5 dibromophenyl]propane, 2,2 - bis - [4 - - (2',3' - dibromopropenoxy) - 3,5 dibromophenyl]propane, 2,4,6 - tribromophenyl 2,3 - dibromophenyl ether, 2,4,6 - tribromophenyl 2,3 - dibromopropyl ether, 2,2 - bis - bromomethyl - 3 bromopropyl carbonate, decabromobiphenyl oxide, octabromobiphenyl, hexabromobenzene, hexabromomethylbenzene, hexabromocyclododecane, commerical chloroparaffin, and the compound of formula
The proportion of such additional flameproofing agent(s) in the total flameproofing agent used may suitably be up to 90% by weight. Preferably, however, the proportion by weight is from 10 to 70%, and more preferably from 15 to 60%.
In the following Tables I to 3, examples of the above-defined compounds of formula I, suitable as flameproofing agents for cellulose acetate, are presented. The Examples following the Tables are to the flameproofed cellulose acetate of the present invention and its methods of production. In these Examples, parts and percentages are by weight.
T a b l e 1
Z cY o I P 3 Y r acY n c, OI t oo cu J 5: 0. formula m.p. 0C I CM CR 0 6 CR3," CR0 ^e CR3 oN t B 2 S Uhl I 2 CR3;c1CR20 7 8 C P P b.p. f k / 2 oN S CR3," ,CR20 3 CR3," ,CR20\ Q ,P11CR2-CCR2Br)3 u o U CR2o/eC3ll7SO Q Q cJ Q U Q c; Q Q d o 03 O1 0 Z / 2 O p-C-C II -iso 125-7! CR CR 0" 2 2 S 5 CR3," CR20\ b.p. 10 CR CR Z hi 0 . U ffi / P-o-CII11-iso < ffi 2 \ ez 51-3 E < , es ~ O O n &verbar; 'I I I~ r rv o ~ X X :z: X Xes oVQ on ow oL v :e 8:s o O O O O O O O O O O w : 2 UXs 6 E; 2 en g x 6 x 2 Q Q o ~ N n < e A T a b l e 1
0 o re re oX o o o &verbar; &verbar; No. formu1 m.p.0 No. formula m.p. 0C 11 CH3,%C 2O p - 100-1 16 H2c/C1120\p CR 'CR cH2o511 ol 3 2$ CR0 a | T a E ns :e : p : O | L =a =V1 3 0N 0N N eS QN CR3 = CRCRO Br5 Ohl OCJ o o o zits CR 'CII hl 1 o 3 2 $ CR3 P 3 T P - 72-3 9 ' | 0/P,,-oC3H7-ffL I CH20 " 2 S E /CII2O,," HC P - 0 -C II -tso otl sCll0 & 'CII 0'11 3 1 20 & P - 0 124-5 2$ Cli v e E O O O O &verbar; O w X :e X t 0N 0N Osq 0N 0N 0N 0N 0 o Xo u Q t X 6 Q Q Q Q \, Sn X X Q X O <
Table 1 No. m.p. -e n n cr h o h C211 CR2O oti 27 ( CR3,,,"CR20 P -OCR2 +2C < CR3)2 F 'CliO ' -OC2R5 164-5 cY (Y o 49 2 V CR3 22 C2N5CR2Op - g CR on r /11 = \/ r 8 C4R9, CHO 2 w Q 28 X +il 3 2 S N CY E SN Br 6 E '2o'; Br 29 ( , T 0 =6 Q=1 0rl 44 F p, X Bo \ 24 CR3,CR2O OI 1 N N N N N CII N u 6 3 2 o Q Q \D c: o u xQ u x s 8 xq x xu 9 25 ( a(3CR2O),p, E 2CII2 125-7 31 ( CR3C/CR2O,P -0-CR2-CR)-2 138-41 z b o o o 26 o :3;ceCu2O%,: -0Cll2-aI22 166-9 CII3,ClI2O% < -CR2-C, ?2 174-? E N c( cr c b + Xe Z ~ &verbar; n $ u X 4 s O O O O O O ~ S S Q Q ts U 3s v S 3: S Q B ~ oN t Q Q S 6 So F o T a b l e 1
-- - - - -- - o u o IP e; [(nC3Rpo2 ; 1=b.5.,P0:12 atm. b ray X 35 [(nC3R72 hl N A 6 Z O 8 ? o: eD v 8 a * O O Q Q Q S S & O n < Table 2
o 0. Q, rl dD 'i; 'i: n x formula o n.p0i:o7 -- eo X.P.0C 36 ONH- P - () - 1 NH-2 2t8-9 42 ,0CR2 il I. ON 2 C 108-9 cr (3 cu 8 ou JXos 37 (N3R}2 on 215-6 u 2 \ H h( Z I(Y o" OCR2 IIf oU oUv, 8 03 1 38 O: NH P 1 ;.: tn Cl 221-3 n-C HO P-C-P OC =vl 2 44 3 7 2 3 7 2 hl -;54 39 (CR3NR}2 P-C-p 45 iC3N7o2;.'-oP5'.{ OC3H =n 2 Oil I I 011 O NH 0CH32 219-220 L I 0 O cu c w (CR2-NH2 0Ps.-o)P1( NRCR2) 2 ot tst ot 2 Oil CY 41 P-C-P 210-21 47 (O)2 r0P5ii0 C \o(3 105 Z z P. o Z z S ~o -o O 9 v z ol &verbar; 0 Dz =O zo X - O v o K o I ~ ~ X o 4 6^t X t o o Table 2
I u o c( > . o o o o J o M.P. - o z o 15-0-P n O2 Oil ? 'SI'S' S s > Cli2C1 55 ) n-C6H L30)i t-o-P15 OC6H13n) 2 oil ,c)(-O s o OCR Oil S S ciai2 2 O SI C112C12 C, o o \o 56 u vz c. ~ n Q Q ~s G Otl =+ r Q N ,, = 6 6 Q P-O-P N 3 U Q n ~ 57 ,' P,5-O-P', 0C2H5 2 oil 51 ( C2R50}2 :,O;S, 0c2H5) 2 oiling pt CR3 CR20 $ S u Uavr V CR0 nin of 0. uq " 00 eVe M: n-C4H902 ;-0-.- 0C4 o ,fl 2 Oil o P;-O;55 0C4N9-n 2 oil " n 53 ( iC4?t,o2;s0ss OC4N,t) 2 Oil B2;c/,"1ll2O,\ P,1-O-,P, ( 0C3)I 7.n)2 Oil he 0120 S te t I w O O :s ~~ O X =sn s ~ o v sus O ~g~ ' ~ S :e 4 O G: I O O A ~ 'JX < T o - en X : ≈ t K: to N H o O b v oP ~ t Table 2
u o - - 60 CH3C / CH20 - N;CH3 Oil 64 flC3N7O\j,0p C2R5 Oil / \ se C \ N c -e S S lose se o o 6 25 25 E C1H5O -0-P OC2N5 Oil Z NO OC N ;~' o \ all C c: uz / v o CR3 S CR3 n , ; s ,CR3 Oil NS SN a u C113 h\ 3 62 r 2 m c? t3O-131.5 0,,-' 131-2 CR3," /ii hl CM 66 p-S-P Z I N 2 Ss CM3 CR3 U ~S ; ' ' O ' 37 P-O-p 63 CR3," / ', ,CH3 Oil CH3 ,CN 20," OCR2," ,CII3 CR S 5 2 3 G \ 6 v So So =n SY X, > Eo I &verbar; o zE I 0, > oN =sn p S O C.:ct.
\evo oe ;s /XX 0 Oo \ Z nS \ n Ss ox O - 2 Q 2 = > s oX n &commat; Q Q UZ g Q d a o o H Table 2
o I I I 0 OI OI oO 00 u &verbar; o =N On c 69 BrCN2 &num;CR2O," ,OCR CR Dr CR3% CR0 m N/C3R1fl C P-S-P 2'C' 2 I('4-165.5 P - 0 P - 118-9 hh CH2O"" 'S'O 'CRflr sh CR2, 2 o'' C3R7-n 0 o | P 4 < &num; l o: X o o o 3 5 w CR20 o CR3 2 , \ NN 00 00 00 cucu curu cucu \/3 2 E I Z 5 E CR3," ,Cl(2O -OP- 76 3'C6CH2:/\P - 0 2 5P, - NH -. CR3 159-6 71 CR3, 9 t60-2 CR3, e 'ci'2si t 7 v, P (e rh N 158-9 Z h h CR o e ,CR20," $2055C'H3 3"'cR2o'; 2 5 s0 72 C rPI QI 'CR ss 2 14 1 I I 73 flCR2&num;pal2O\ - 0 P - N6C3R7fl 78 ;Cii20/ 5P5 - 0 - 118-9 s o E s Q v = U o 7 o c v o v - o o o N 84 UM o o Wo s sN o' ;o o o o o - - , E=Js sU es Q U Q N tJ is e Q < sa -c sU Et Table 2
, so . formula H.P.C 79 ( /CHZO, 2 CH '3c, .P' Tz l?r4-S BrCH2 CH2 S 2 2 S S'S \CH CH , CH C,tt,-n 80 { 3xC' 2 z P ~ 2 P Ns 3 105-6 \ 3 CH20 \C?H-n 3 Ctl,O S S , r 1 81T7 ICH?O 1 ICH3 B1 (5(CH20 lf7-8 \CH9 S S I Table 3
cltine point ( C) No. 1 formula M1 /. \ 2)CCH20 BrCH2 CBZO/ p 4 o 174-175 wBrCH2 Cil20 o 7 2 , - . . .
3:Clnl,o,P BJ ( C/CIIIO/ 1 sr: /C1CH2 CH20s \ r99-2000 ,Cs Z P H 0 199-200 CIIZO/ Cil2 S 22 84 ClaIZ Ctl ,CH,O 134-136 \c,"; /Y\ 85 (CH C/ CH . f) 139-1400 r C2HS sCH20 s 139-140 86 VC2ll5 CH20 S .
87 I /Y\ 87 VC3117 CH20 88 Lf c :,Hg\C/CH20O -(iquid) CII,O 2 Table 3
- z - - - | No. formula vlelting point C B9 ( z CH2 S 2 240-242 3\C/ 89 CHZO)/ 2 = 0 U1-Us0 90 t C crr,cl ) 1 rc/ :C( L 90 11., 1CH, 'CHZC1 Ic ctr - ctr, 91 (r- CKo 2=co 2 O p X o 228 vith CH2- CH2 al2 S J2 docompszsition .
92 / 1 E 0 106-1080 C CIE U S L 7 CH3 / CR2 \ 1, 157-158 93 \CHj2 \3 I 1CZHS\ / a'20 \ licluid) C 1 / \QfO/ 94 t H :3H7 Hs f - CR0 r59-1600 95 ( Cg3 %{3 )2 (H2C\ C --C .
96 161-1630 iC;alo t . rHC w 2s C / 2 x 4 o 239-241 2 Br 1400 vith > CH - Cb a1,6 1( oCR Cl12s Cv CH,O/ ) 0 140 with ctl,- CH2 Example I 2 parts of cellulose 22 acetate powder are dissolved in 8 parts of acetone with stirring. To the solution is slowly added 0.02 part of the compound No. 31 of Table I with simultaneous stirring of the mixture, and stirring is continued until the added compound has dissolved. The resulting mixture is poured onto a glass plate and then smoothed out to a fine film. After the acetone has evaporated off, the plasticized film is freed from the glass plate and then dried in an oven at 85 C for 30 minutes.
The film can be tested for flameproofing properties by measurement of the Limiting Oxygen Index (LOI) according to the method of Fenimore and Martin (see Modern Plastics, November 1966), or according to the German Industrial Standard No. 53906 (vertical test).
In an analogous manner the compounds Nos I to 30 and 32 to 34 of Table I and all the compounds of Tables 2 and 3 are used to flameproof cellulose 2T acetate and can be tested for their flameproofing effects.
Example 2 2 parts of cellulose 2T acetate powder are dissolved in 8 parts of acetone with stirring. To the stirred solution are slowly added 0.02 part of 2,2-bis(4-(2',3'dibromopropenoxy) - 3,5 - dibromophenyl) - propane and 0.02 part of the compound No. 26 of Table 1, and stirring is continued until the added compounds have dissolved. The resulting mixture is then worked into a film by the method described in Example I, and the film can be tested for flameproofing properties by the method also indicated in Example 1.
In an analogous manner the compounds Nos. l to 25 and 27 to 34 of Table I and all the compounds of Tables 2 and 3 are used to flameproof cellulose 22 acetate and can be tested for their flameproofing effects.
Example 3 26 parts of cellulose 2T acetate powder are dissolved in 74 parts of acetone with stirring, after which 0.52 part of the compound No. 83 of Table 3 is introduced into the solution. The mixture is stirred at a stirrer speed of 500 revolutions per minute, during which the temperature rises to 40 C and a clear solution is produced.
The resulting solution is dry spun to fibres, and the fibres are made into knitted fabric with a surface weight of 250 g/m2. The knitted fabric is then washed once at 60 C in a household washing machine and conditioned for 24 hours at 23 C and at a 50 relative air humidity. By the methods indicated in Example I the knitted fabric can be tested for flameproofing properties.
In an analogous manner the compounds Nos 82 and 84 to 98 of Table 3 and all the compounds of Tables I and 2 are used to flameproof cellulose 22 acetate and can be tested for their flameproofing effects.
Example 4 15 parts of cellulose triacetate are dissolved in a mixture of 76.5 parts of methylene chloride and 8.5 parts of methanol with stirring. To the solution is slowly added 0.75 part of the compound No. 83 of Table 3 with simultaneous stirring of the mixture, and stirring is continued until the added compound has been uniformly distributed in the solution. The resulting mixture is poured onto a glass plate and then smoothed out to a fine film. After evaporation of the solvents, the film is freed from the glass plate and then dried in an oven at 80 C for 2 hours. The film can be tested for flameproofing properties by the method indicated in Example 1.
In an analogous manner, the compounds Nos. 82 and 84 to 98 of Table 3, and all the compounds of Tables I and 2 are used to flameproof cellulose triacetate and can be tested for their flameproofing effects.

Claims (55)

WHAT WE CLAIM IS:-
1. Flameproofed cellulose acetate including, as a flameproofing agent, not more than S0o (by weight of cellulose acetate) of one or more compounds of formula I
in which each R, independently, is a radical
Y is oxygen or sulphur, Q is a radical OR4 (c)
wherein each R, independently, and Y, independently, are as defined above. each R" independently. is methyl; ethyl or propenyl, each unsubstituted or substituted with up to 3 halogen atoms or with a (C1~6)alkoxy radical; (C3-12)alkyl or (C4-12)alkenyl, each unsubstituted or substituted with up to 4 halogen atoms; (C5-8)cycloalkyl or (C5-8)cycloalkyl-(C1-4)alkyl, containing 7-9 carbon atoms in toto, each unsubstituted or ring substituted with 1 or 2 halogen atoms; or phenyl or phenyl-(C1-4)alkyl, each unsubstituted or aromatically substituted with up to 5 halogen atoms, with up to 3 (C,~3)alkyl radicals, or with up to 3 (C,~3)alkoxy radicals, or two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f),
and each of the other two moieties R" when present, independently, is a radical as defined above or the other. two moieties R" when present, together form a second radical (f), independent from the first radical (f) either the or each R2, independently, is (C,~4)alkyl, cyclohexyl or benzyl; or phenyl, unsubstituted or substituted with l or 2 chlorine atoms of which at most one can occupy an ortho-position, or with a bromine atom in the para-position, or with up to 2 (C,~3)alkyl or up to 2 (C,~3)alkoxy radicals, the aggregate of the carbon atoms thereof not exceeding 3, and the or each R3, independently, is (C,~4)alkyl or hydrogen, or any R2 and R3, independently from any other R2 and R3, together with the nitrogen atom to which they are bound, form a 5- or 6-membered saturated heterocyclic ring which may optionally contain as a ring member an oxygen or sulphur atom, or a second nitrogen atom to which is bound a (C,~4)alkyl radical, R4 is (C2~,8)alkyl, unsubstituted or substituted with up to 3 halogen atoms or with a (Ct~,)alkoxy radical; (C3~,0)alkenyl, unsubstituted or substituted with up to 3 halogen atoms; cyclohexyl- benzyl, or phenyl, unsubstituted or substituted with up to 5 substituents selected from chlorine and bromine atoms and methyl and ethyl groups Rs is ethylene, straight or branched chain (C3~,0)alkylene or straight or branched chain (C4~,0)alkenylene, each having at least two bridging carbon atoms and being unsubstituted or substituted with l or 2 halogen atoms; straight chain (C4~,0)alkynylene; or a divalent radical selected from those of formulae
Z, or each Z, is oxygen or sulphur, n is zero or l, A is a radial (a), as defined above, or a radical
X is oxygen or sulphur, either each R6 and R7, independently, is hydrogen, (C1-4)alkyl, -CH2Cl, -CH2Br or phenyl, not more than one being phenyl, or any R6 and R7 together with the carbon atom to which they are bound, independently from any other > CR6R7 moiety, form a cyclohexylidene, cyclohexenylidene 3,4-dibromocyclohexylidene ring, each R8 and R10, independently, is hydrogen or (C1-4)alkyl, each R9, independetly, is hydrogen or methyl, each of m, m1, and m2 is zero, 1, 2, 3 or 4, the sum of m1 amd m2 not exceeding 4, each of n1 and n2, independently, is an integer from 1 to 6, X IS oxygen or sulphur, either R" is methyl; ethyl, unsubstituted or substituted with a halogen atom; propyl, unsubstituted or substituted with l or 2 halogen atoms; (C4~12)alkyl, unsubstituted or substituted with up to 3 halogen atoms cyclohexyl; benzyl; or phenyl, unsubstituted or substituted with l or 2 chlorine atoms, or with a bromine atom in the para-position and/or in both cases with up to 2 (C,~3)alkyl and/or (C1~3)alkoxy radicals, the aggregate of the carbon atoms thereof not exceeding 3, and R12 is hydrogen;: methyl; ethyl, unsubstituted or substituted with a halogen atom; propyl, unsubstituted with up to 2 halogen atoms; (C4-12)alkyl, unsubstituted or substituted with up to 3 halogen atoms; cyclohexyl; benzyl; or phenyl, or R11 and R12, together with the nitrogen atom to which they are bound, form a 5- or 6-membered, saturated heterocyclic ring which may contain as a ring member an oxygen or sulphur atom, or a second nitrogen atom to which is bound a (C,~4)alkyl radical, th the provisos: (i) when Q is a radical (c) or (d), then neither R can be a radical (b), (ii) when Q is a radical (c) and R4 signifies (C2~,8)alkyl substituted with (C1 6)alkoxy, then such alkoxy substituent cannot be on the (r-position of the alkyl radical, (iii) when QW is a radical (c), then the OR1's signified by the two R's can only form together a radical
(iv) when Q is a radical (d), R6 signifies optionally halogen-substituted, branched chain C6 alkylene and both pairs of OR,.,, independently signify radicals
then R6 can only signify branched chain C6 alkylene substituted with at least one halogen atom (v) when Q is a radical (e), and at least one of the Y's and X is oxygen, then Z can only be oxygen, (vi) when two radicals 8b) are attached to a phosphorous atom and Y attached to that same phosphorus atom is sulphur, then both the moieties R2 in these radicals (b) are (C, 4)alkyl, (vii) when n is l, or when n is zero and R2 in any radical (b) is (C, 4)alkyl, then each R3 present, or R3 in that same radical (b), respectively, can only be (C1-4)alkyl, (viii) at least one of R6, R7, R8, R9 and R10 in any radical (f) is other than hydrogen, and (ix) when each of R6 and R7, independently, in any radical (f) is -CH2Cl or -CH2Br, or both R6 and R7 together with the carbon atom to which they are bound form a cyclohexylidene, cyclohexenylidene or 3,4 dibromocyclohexylidene ring, then each of R8, R9 and R10 in the same radical (f) is hydrogen.
2. Flameproofed cellulose acetate according to Claim 1, including as flameproofing agent, one or more compounds of formula Ia,
in which R4, R6, R7, R8, R9, R10 and Y are as defined in Claim 1, with the provisos (ii), (Viii) and (ix) therein.
3. Flameproofed cellulose acetate according to Claim 1, including, as a flameproofing agent, one or more compounds of formula Ib,
in which each R1, independently, and/or the or both radicals (f) formed by the or both of two moieties R1 bound via oxygen atoms to the same phosphorous atom, R5 and Y are as defined in Cklaim 1, with the provisos (iv), (viii) and (ix) therein.
4. Flameproofed cellulose acetate according to Claim 1, including, as a flameproofing agent, one or more compounds of formula Ic,
in which each R, independently, Z or each Z, n, A, X and Y are as defined in Claim 1, with the provisos (v), (vi), (vii), (viii) and (ix) therein.
5. Flameproofed cellulose acetate according to Claim 2, in which R4 is optionally substituted alkenyl or phenyl.
6. Flameproofed cellulose acetate according to Claim 3, in which either any R1 is optionally substituted alkyl, cycloalkyl, phenyl or phenylalkyl, or two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f).
7. Flameproofed cellulose acetate according to Claim 6, in which either any R, is optionally substituted alkyl, cycloalkyl or phenyl, or two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f).
8. Flameproofed cellulose acetate according to Claim 7, in which either any R, is optionally substituted alkyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f).
9. Flameproofed cellulose acetate according to Claim 8, in which two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f).
10. Flamenroofed cellulose acetate according to any of Claims 3 and 6 to 9, in which Rs is un^substituted or substituted alkylene or alkenylene, alkynylene, or more of the divalent radicals
I I . Flameproofed cellulose acetate according to Claim 4, in which each R is a radical --OR, and either any R, is optionally substituted alkyl, or alkenyl cycloalkyl, phenyl, or phenylalkyl, or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f).
12. Flameproofed cellulose acetate according to Claim 11, in which each R is a radicalOR1, the two moieties Y are both sulphur, Z is oxygen, n is zero and either any R1 is optionally substituted alkyl, cycloalkyl or phenyl, or two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f).
13. Flameproofed cellulose acetate according to Claim 12, in which any R, is optionally substituted alkyl.
14. Flameproofed cellulose acetate according to Claim 11, in which each R is a radicalOR1, the two moieties Y and Z are all sulphur, n is zero and either any R is optionally substituted alkyl or two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f).
15. Flameproofed cellulose acetate according to Claim 14, in which two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f).
16. Flameproofed cellulose acetate according to Claim l l, in which each R is a radicalOR1. the two moieties Y are both sulphur, Z is oxygen, n is l, A is a radical (g) and either any R1 is optionally substituted alkyl or two moieties R, bound via oxygen atoms to the same phosphorus atom form a radical (f).
17. Flameproofed cellulose acetate according to Claim 16, in which two moieties R1 bound via oxygen atoms to the same phosphorus atom form a radical (f).
18. Flameproofed cellulose acetate according to Claim 4, in which each R is a radicalNR2R3 and any R2 is alkyl or optionally substituted phenyl.
19. Flameproofed cellulose acetate according to Claim 18, in which any R2 is optionally substituted phenyl.
20. Flameproofed cellulose acetate according to any one of Claims 4, 18 and l9, in which each R is a radicalNR2R3 and any R3 is hydrogen.
21. Flameproofed cellulose acetate according to any one of Claims I to 12, and 14 to 17, in which R6 in any radical (f) is alkyl,CH2CI orCH2Br.
22. Flameproofed cellulose acetate according to Claim 21, in which R6 in any radical (f) is alkyl.
23. Flameproofed cellulose acetate according to any one of Claims I to 12, 14 to 17, 21 and 22, in which R7 in any radical (f) is alkyl,CH2CI orCH2Br.
24. Flameproofed cellulose acetate according to Claim 23, in which R7 in any radical (f) is alkyl.
25. Flameproofed cellulose acetate according to any one of Claims I to 12, 14 to 17 and 21 to 24, in which R8 in any radial (f) is hydrogen.
26. Flameproofed cellulose acetate according to any one of Claims 1 to 12, 14 to 17 and 21 to 25, in which R9 in any radical (f) is hydrogen.
27. Flameproofed cellulose acetate according to any one of Claims 1 to 12, 14 to 17 and 21 to 26, in which R10 in any radical (f) is hydrogen.
28. Flameproofed cellulose acetate according to any of Claims 4, 11,18, 19 and 20, and Claims 21 to 27 when appendant to Claim 4 and not appendant to any of Claims 12 and 14 to 17, in which n is zero.
29. Flameproofed cellulose acetate according to any of Claims 2, 3 and 5 to 10, and Claims 21 to 27 when appendant to any one of Claims 2, 3 and 5 to 10 and not appendant to any of Claims 4, II, 12 and 14 to 17, in which Y is sulphur.
30. Flameproofed cellulose acetate according to Claim 1, including, as a flameproof ng agent, one or more compounds of formula I',
in which Q' is a radicalOR'4 (c') or
each R1' independently, is ethyl; chloroethyl; bromoethyl; (C3-12)alkyl, unsubstituted or substituted with up to 3 chlorine atoms or up to 3 bromine atoms; cyclohexyl; phenyl, unsubstituted or substituted with up to 3 halogen atoms or up to 3 methyl groups; or benzyl, or two moieties R'1 bound via oxygen atoms to the same phosphorus atom form a radical (f'),
and each of the other two moieties R'1, when present, independently, is a radial as defined above, or the other two moieties R'1, when present together form a second radical (f'), independent from the first radical (f'), R'4 is (C2~6)alkyl, unsubstituted or substituted with up to 3 halogen atoms or a methoxy group; 2,3 - dibromopropen - 2 - yl; cyclohexyl: benzyl; or phenyl, unsubstituted or substituted with up to 5 substituents selected from chlorine and bromine atoms and methyl and ethyl groups, R's is ethylene; straight or branched chain (C3~6)alkylene, having at least 2 bridging carbon atoms and being unsubstituted or substituted with I or 2 chlorine atoms or I or 2 bromine atoms, or a divalent radical selected from those of formulae -CH2CH=CHCH2- -CH2C(Cl)=C(Cl)CH2 -CH2C(Br)=C(Br)CH2- -CH2C=CCH2
each R6' and R7', independently, is (C1-4)alkyl, -CH2Cl or -CH2Br, or any R6' and R7' together with the carbon atom to which they are bound, independently from any other > CR6'R7' moiety, form a cyclohexylidene, cyclohexenylidene or 3,4 - dibromocyclohexylidene ring, and m iszero, 1, 2, 3 or 4, with the provisos: (i) when Q' is a radical (c') and R'4 signifies (C2~6)alkyl substituted with a methoxy group, then such methoxy substituent cannot be on the &alpha;-position of the alkyl radical, (ii) when Q' is a radical (c')m, then the OR1's can only form together a radial (f'), and (iii) when Q' is a radical (d'), R5' signifies optionally halogen-substituted, branched chain C5 alkylene and both pair of OR1' s, independently, signify radicals
then R5' can only signify branched chain C5-alkylene substituted with at least one halogen atom.
31. Flameproofed cellulose acetate according to Claim 4, including, as a flameproofing agent, one or more compounds of formula I",
in which each R", independently, is a radical OR"1 (a') or
Y is oxygen or sulphur, each R"1, independently, is ethyl: chloroethyl; bromoethyl; (C3 6)alkyl. unsubstituted or substituted with up to 3 chlorine atoms or up to 3 bromine atoms; (C3~6)alkenyl, unsubstituted or substituted with I or 2 chlorine atoms or I or 2 bromine atoms; cyclohexyl; phenvl. unsubstituted or substituted with up to 3 chlorine atoms with a bromine atom in the para-position, or with up to 3 methyl groups; or benzyl, unsubstituted or aromatically substituted with up to 3 chlorine atoms or with a bromine atom in the para-position, or two moieties R''1 bound via oxygen atoms to the same phosphorus atom form a radical (f"),
and each of the other two moieties R1" when present, independently, is a radical as defined above or the other two moieties R1", when present, together form a second radical (f"), independent from the first radical (f"), the or each R'2, independently, is (C1~3)alkyl; or phenyl, unsubstituted or substituted with a chlorine atom, with a bromine atom in the para position, or with a methyl group the or each R'3, independently, is (C;~3)alkyl or hydrogen, Z, or each Z, is oxygen or sulphur, n IS zero or 1, X is oxygen or sulphur, either R'11 is (C,~4)alkyl, cyclohexyl, benzyl or phenyl, and R',2 is hydrogen, (C,~4)alkyl, cyclohexyl, benzyl or phenyl, or R'11 and R',2, together with the nitrogen atom to which they are bound, form a piperidino or or morpholino ring, either each R' and each R7' independently, is (C1-4)alkyl, -CH2Cl or -CH2Br, or any R'6 and R'7, together with the carbon atom to which they are bound, independently from any other > CR6'R7' moiety, form a cyclohexylidene, cyclohexenelydene or 3,4-dibromocyclohexylidene ring, with the provisos: (i) when at least one of the two Y's and X is oxygen, then Z can only be oxygen, (ii) when two radicals (b') are attached to a phosphorus atom and Y attached to that same phosphorus atom is sulphur, then both the moieties R'2 in those radicals (b') are (C1~3)alkyl, (iii) only when one of the moieties R'2 and R'3 bound to the same nitrogen atom in a radical (b') is ethyl or propyl, can the other be ethyl or propyl, and (iv) when n is I, or when n is zero and R'2 in any radical (b') is (C1~3)alkyl, then each of R'3 present, or R'3 in that some radical (b'), respectively, can only be (C1~3)alkyl.
32. Flameproofed cellulose acetate according to Claim 2, including, as a flameproofing agent, one or more compounds of formula I'a,
in which Rf4a is 2,3-dibromopropen-2-yl; or phenyl, unsubstituted or substituted with up to 3 chlorine atoms, up to 3 bromine atoms or up to 3 methyl groups, and each of R6a' and R7a', independently, is (C1-3)alkyl, -CH2Cl or -CH2Br, with the proviso that when of R6a' and R7a' is -CH2Br, then the other is other thanCH2CI.
33. Flameproofed cellulose acetate according to Claim 3, including, as a flameproofing agent, one or more compounds of formula I'b,
in which R1b' is n- or isopropyl, unsubstituted or substituted with 1 or 2 chlorine atoms or 1 or 2 bromine atoms, (C4-6)alkyl, unsubstituted or substituted with up to 3 chlorine atoms or with up to 3 bromine atoms; cyclohexyl; or phenyl, and R5b' is straight chain (C3-5)alkylene, unsubstituted or substituted with 1 or 2 chlorine atoms or 1 or 2 bromine atoms; or a divalent radical selected from those of formulae
34. Flameproofed cellulose acetate according to Claim 3, including, as a flameproofing agent, one or more compounds of formula I'c,
in which R'6a and Rf7a are as defined in Claim 32, and R'sb is as defined in Claim 33.
35. Flameproofed cellulose acetate according to Claim 4, including as a flameproofing agent, one or more compounds of formula Ia",
in which R"2a is phenyl, unsubstituted or substituted with a chlorine atom in the para-position or with a methyl group.
36. Flameproofed cellulose acetate according to Claim 4, including, as a flameproofing agent, one or more compounds of formula I"b,
in which each R"1b, independently. is n- or isopropyl. unsubstituted or substituted with I or 2 chlorine atoms or with I or 2 bromine atoms: (C4 6)alkyl, unsubstituted or substituted with up to 3 chlorine atoms or with up to 3 bromine atoms, cyclohexyl; or phenyl, unsubstituted or substituted with a methyl group, or two moieties R1b" bpound via oxygen atoms to the same phosphorus atom form a radical (f"')
and each of the other two moieties Rtb, independently, is a radical as defined above or the other two moieties together form a second radical (f"'), independent from the first radical (f"'), and each R6b" and R7b", independnetly, is (C1-3)alkyl, -CH2Cl or -CH2Br, or any R6b", together with the carbon atom to which they are bound, independently from any other > CR6b"R7b" moiety, form a 3,4 dibromocyclohexylidene ring, with the proviso that when one of R6b" and R7b" in any radical (f"') is -CH2Br, then the other than -CH2Cl.
37. Flameproofed cellulose acetate according to Claim 4, including, as a flameproofing agent, one or more compounds of formula Ic", flameproong
in which each R1c" is propyl or butyl, or each of the two sets of two moieties R1c" bound via oxygen atoms to the same phosphorus atom form a radical (f"'), as defined in Claim 36.
38. Flameproofed cellulose acetate according to Claim 4, including, as a flameproofing agent, one or more compounds of formula I"d,
in which each R1d" is n- or iso-propyl, unsubstituted or substituted with 1 or 2 chlorine atoms or with 1 or 2 bromine atoms; or (C4-6)alkyl, or each of the two sets of two moieties R1d" bound via oxygen atoms to the same phosphorus atom for a radical (f"), as defined in Claim 36, X is oxygen or sulphur, and either R"11 is (C1~4)alkyl, cyclohexyl, or beryl, and R",2 is hydrogen or (C1~4)alkyl, or R"11 and R"12, together with the nitrogen atom to which they are bound, form a piperidino or morpholino ring.
39. Flameproofed cellulose acetate according to Claim I, including, as a flameproofing agent, one or more compounds selected from the group consisting of those of formulae,
and
40. Flameproofed cellulose acetate according to Claim 1, including, as flameproofing agent, one or more compounds substantially as herein described with reference to any one of the compounds Nos. I to 25, 27 to 30, 33 to 81 and 84 to 98.
41. Flameproofed cellulose acetate according to any preceding claim, in which the cellulose acetate is cellulose 2+ acetate with an acetyl value of 53 to 56% as chemically bound acetic acid, or cellulose triacetate with an acetyl value of 60 to 62.5 as chemically bound acetic acid.
42. Flameproofed cellulose acetate according to any preceding claim, in which the amount of said flameproofing agent is at least 0.1 of the weight of the cellulose acetate substrate.
43. Flameproofed cellulose acetate according to Claim 42, in which the amount is from 0.5 to 5%.
44. Flameproofed cellulose acetate according to Claim 43, in which the amount is from 0.5 to 2%.
45. Flameproofed cellulose acetate according to any preceding claim, in which there is present as a further flameproofing agent one or more compounds selected from bis- (2,3 - dibromopropyl)- terephthalate, 2,2- bis- [4- (2',3' dibromopropoxy)- 3,5 - dibromophenyllpropane, 2,2-bis- [4- (2',3' dibromopropenoxy) - 3,5 - dibromophenyllpropane, 2,4,6-tribromophenyl 2,3 dibromopropenyl ether, 2,4,6-tribromophenyl 2,3 - dibromopropyl ether, 2,2 bis- bromomethyl- 3 - bromopropyl carbonate, decabromobiphenyl oxide, octabromobiphenyl, hexabromobenzene, hexabromomethylbenzene, hexabromocyclododecane, commercial chloroparaffin, and the compound of formula
46. Flameproofed cellulose acetate according to Claim 45, in which the proportion of the further flameproofing agent is from 10 to 70 of the total flameproofing agent present by weight.
47. Flameproofed cellulose acetate according to Claim 46, in which the proportion is from 15 to 60%.
48. Flameproofed cellulose acetate according to Claim 1, substantially as herein described with reference to any one of Examples I to 4.
49. A method of producing flameproofed cellulose acetate comprising incorporating in the cellulose acetate not more than 5% (by weight of cellulose acetate) of one or more compounds, as defined in any one of Claims 1 to 40, as the flameproofing agent.
50. A method according to Claim 49, comprising removing the solvent from a solution of cellulose acetate in the solvent containing a flameproofing effective amount of one or more compounds indicated in any one of Claims I to 40 with simultaneous shaping of the cellulose acetate containing the incorporated flameproofing agent as it comes out of the solution.
51. A method according to Claim 50, in which the cellulose acetate is cellulose 2+ acetate with an acetyl value of 53 to 56% as chemically bound acetic acid, or cellulose triacetate with an acetyl value of 60 to 62.5% as chemically bound acetic acrid.
52. A method according to Claim 51, in which the solvent employed is, when the cellulose acetate is cellulose 2+ acetate, acetone and, when the cellulose acetate is cellulose triacetate, methylene chloride.
53. A method according to any one of Claims 49 to 52, in which the amount of the one or more compounds used is in the range 0.5 to 5% of the weight of the cellulose acetate substrate.
54. A method according to Claim 53, in which the flameproofing amount of the one or more compounds is in the range 0.5 to 2% of the weight of the cellulose acetate substrate.
55. A method according to Claim 49, substantially as described herein with reference to any one of Examples I
GB15154/78A 1977-04-21 1978-04-18 Flame-proofed cellulose acetate Expired GB1598744A (en)

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CH495277 1977-04-21

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0437335A1 (en) * 1990-01-12 1991-07-17 Rohm And Haas Company Dithiopyrophosphates and their use as pesticides
WO1992005219A1 (en) * 1990-09-26 1992-04-02 Eastman Kodak Company Formulations of cellulose esters with arylene-bis(diaryl phosphate)s
US5219510A (en) * 1990-09-26 1993-06-15 Eastman Kodak Company Method of manufacture of cellulose ester film
FR2691709A1 (en) * 1992-06-02 1993-12-03 Ciba Geigy Ag Trisamidodithionodiphosphates.
AT399890B (en) * 1990-09-04 1995-08-25 Sandoz Ag AQUEOUS DISPERSIONS OF FLAME-RETARDANT COMPOUNDS AND METHOD FOR THE FLAME-RETARDANT EQUIPMENT OF REGENERATED CELLULOSE
WO2008037709A1 (en) * 2006-09-27 2008-04-03 Opco Gmbh Fireproof sheet and method for producing it
US8466096B2 (en) 2007-04-26 2013-06-18 Afton Chemical Corporation 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0437335A1 (en) * 1990-01-12 1991-07-17 Rohm And Haas Company Dithiopyrophosphates and their use as pesticides
AT399890B (en) * 1990-09-04 1995-08-25 Sandoz Ag AQUEOUS DISPERSIONS OF FLAME-RETARDANT COMPOUNDS AND METHOD FOR THE FLAME-RETARDANT EQUIPMENT OF REGENERATED CELLULOSE
WO1992005219A1 (en) * 1990-09-26 1992-04-02 Eastman Kodak Company Formulations of cellulose esters with arylene-bis(diaryl phosphate)s
US5104450A (en) * 1990-09-26 1992-04-14 Eastman Kodak Company Formulations of cellulose esters with arylene-bis(diaryl phosphate)s
US5219510A (en) * 1990-09-26 1993-06-15 Eastman Kodak Company Method of manufacture of cellulose ester film
FR2691709A1 (en) * 1992-06-02 1993-12-03 Ciba Geigy Ag Trisamidodithionodiphosphates.
GB2267494A (en) * 1992-06-02 1993-12-08 Ciba Geigy Ag Trisamidithionodiphosphates
US5360563A (en) * 1992-06-02 1994-11-01 Ciba-Geigy Corporation Trisamidodithionodiphospates
GB2267494B (en) * 1992-06-02 1995-09-20 Ciba Geigy Ag Trisamidodithionodiphosphates
WO2008037709A1 (en) * 2006-09-27 2008-04-03 Opco Gmbh Fireproof sheet and method for producing it
US8466096B2 (en) 2007-04-26 2013-06-18 Afton Chemical Corporation 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions

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