Polymer composition comprising phosphonate flame retardant
Compounds containing polymer material and a phosphorous flame protection agent on the basis of an aminomethyl bisphosphonate, a method for manufacturing the compound, the use of the flame retardant, and selected structures of the flame retardant are disclosed.
1 . A composition comprising a polymer material and a halogen-free flame retardant contained and/or bound therein in a quantity of 1 to 40% by weight in relation to the entire composition, wherein the flame retardant is a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt or a mixture of the aforementioned:
wherein
(N-i) R 1 and R 2 are identical or different substituents and are selected from the group consisting of linear, branched, or cyclic alkyls, alkenyls and alkinyls, unsubstituted and alkyl-substituted phenyls, mononuclear and multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl, or aryl alcohols, or
(N-ii) R 1 and R 2 together, including the N atom, form a saturated or monounsaturated or polyunsaturated heterocycle with 4-8 ring atoms, selected from carbon, oxygen, sulfur, phosphorus, silicon, and nitrogen,
and wherein —X— is an oxygen atom, —O—, or —X— is a single bond, and
wherein R 3 , R 4 , R 5 and R 6 are identical or different substituents and are selected from
(P-i) the group consisting of H, linear, branched, or cyclic alkyls, alkenyls and alkinyls, unsubstituted and alkyl-substituted phenyls, multinuclear aromatics having up to 4 nuclei, mononuclear or multinuclear heteroaromatics having up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, of the following structures (III) and (IV), where n=0 to 100,
and cations wherein the cation is Na + , K + , Mg 2+ , Ca 2+ , B 3+ , Al 3+ , Zn 2+ , NH 4+ or the ammonium ion of an amine compound, selected from the group consisting of melamine or its condensation products, urea, guanidine, morpholine, and piperazine, and/or
(P-ii) when —X— is an oxygen atom, —O—, —OR 3 and —OR 4 together and/or —OR 5 and —OR 6 together and/or —OR 3 and —OR 5 together and/or —OR 4 and —OR 6 together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic acid anhydride having a ring size of 4-10 atoms, and/or
(P-iii) when —X— is a single bond, —R 3 and —OR 4 and/or —R 3 and —OR 5 together, including the P atom of the phosphinate group, form a cyclic phosphinic acid ester or a cyclic phosphinic acid anhydride having a ring size of 4-10 atoms and/or —OR 5 and —OR 6 and/or —OR 4 and —OR 6 together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic acid anhydride having a ring size of 4-10 atoms, wherein
A.) one of the substituents R 1 to R 6 or
B.) one of the cycles formed when
1) The substituents R 3 -R 6 form a cyclic phosphinic or phosphonic acid ester according to (P-ii) or (P-iii), or
2) The substituents R 3 -R 6 form a cyclic phosphinic or phosphonic acid anhydride according to (P-ii) or (P-iii), or
3) The substituents R 1 and R 2 form a heterocycle according to (N-ii),
has a first uncharged or negatively charged functional group that has a heteroatom selected from the group consisting of P, O, N, S, I, CI, Br, F,
wherein the functional group is not-OH, and for the case that one of the cycles according to 1) to 3) has the functional group, the ring atoms of the cycles are substituted with the functional group or with a substituent that has the functional group, and
wherein the term “halogen-free” means that the total halogen content is <1000 ppm by weight.
2 . The composition according to claim 1 , wherein at least one of the substituents R 1 to R 6 or any of the cycles formed by the substituents R 1 to R 6 have at least one further functional group that has a heteroatom selected from the group consisting of N, S, O, Si, I, Cl, Br, F and/or an alkene or alkine group.
3 . The composition according to claim 1 , wherein the first functional group is selected from the group consisting of —NH 2 , —NHR, —NR 2 , —OR, ═O, —SH, —SR, —COOH, —COOR, —OCN, —I, —Cl, —Br, —F, —N 3 , epoxy, lactam, lacton, aziridine, glycolide, oxazoline, and ether, where R=alkyl, alkenyl, alkinyl or aryl and x+y=3.
4 . The composition according to claim 1 , wherein the flame retardant has a covalent bond to the polymer material.
5 . The composition according to claim 1 , wherein R 1 and R 2 are identical substituents.
6 . The composition according to claim 1 , wherein the flame retardant is dry, which means its water content is <0.5% by weight, and reaches a loss of mass of 10% by weight starting at a temperature of 180° C.
7 . The composition according to claim 1 , wherein the flame retardant has a phosphorus content, which is at least 10.0% by weight.
8 . The composition according to claim 1 , wherein at least one of the groups R 3 , R 4 , R 5 and Re are a cation or H, wherein the cation is Na + , K + , Mg 2+ , Ca 2+ , B 3+ , Al 3+ , Zn 2+ , NH 4+ or the ammonium ion of an amine compound, selected from the group consisting of melamine or its condensation products, urea, guanidine, morpholine, and piperazine.
9 . The composition according to claim 1 , wherein the polymer material contains the flame retardant in a quantity of at least 3% by weight and in a quantity of not more than 35% by weight, in relation to the entire composition.
10 . The composition according to claim 1 , wherein the composition comprises at least one further flame-retardant component that is selected from nitrogen bases, melamine derivates, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic phosphonates and derivates of the aforementioned compounds.
11 . A method for producing a composition according to claim 1 , wherein the flame retardant is a co-condensation component or a co-addition component of the polymer material that is incorporated into the polymer material during production by polycondensation or polyaddition.
12 . The composition according to claim 2 , wherein the further functional group are selected from the group consisting of —NH 2 , —NHR, —NR 2 , —OH, —OR, ═O, —SH, —SR, —COOH, —COOR, —OCN, —SIR x H y , —I, —Cl, —Br, —F, —N 3 , epoxy, lactam, lacton, aziridine, glycolide, oxazoline, ether, alkenylene and alkinylene, where R=alkyl, alkenyl, alkinyl or aryl and x+y=3.
13 . The composition according to claim 12 , wherein the further functional group is an alkenyl or epoxy group.