POLYMER COMPOSITION COMPRISING PHOSPHONATE FLAME RETARDANT

Abstract

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.

Claims

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: ##STR00106## wherein (N-i) R.sup.1 and R.sup.2 are identical or different substituents and are selected from the group consisting of linear, branched, or cyclic alkyles, alkenyles and alkinyles, unsubstituted and alkyl-substituted phenyles, mononuclear and multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyles, allyl, alkyl, or aryl alcohols, or (N-ii) R.sup.1 and R.sup.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, wherein these nitrogen atoms are preferably substituted on the heterocycle—if it has nitrogen atoms as ring atoms—with H, an alkyl, an aryl, or a methylbisphosphonate group having the following structure (II), ##STR00107##  and wherein on the heterocycle—if it has carbon, phosphorus, or silicon as ring atoms—these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, —NH.sub.2, —NHR, —NR.sub.2, —OH, —OR, ═O, —I, —Cl, —Br, F, —N.sub.3, —SH, —SR, —OCN, epoxy, lactam, lacton, aziridin, glycolide, oxazolin, ether, alkenylene, and alkinylene, —SiR.sub.xH.sub.y, where R=alkyl, alkenyl, alkinyl or aryl and x+y=3, and wherein —X— is an oxygen atom, —O—, or —X— is a single bond, and wherein (P-i) R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are identical or different substituents and are selected from the group consisting of H, linear, branched, or cyclic alkyles, alkenyles and alkinyles, unsubstituted and alkylsubstituted phenyles, multinuclear aromatics having up to 4 nuclei, mononuclear or multinuclear heteroaromatics having up to 4 nuclei, silyles, allyl, alkyl or aryl alcohols, of the following structures (III) and (IV), where n=0 to 100, ##STR00108##  and cations wherein the cation is Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, B.sup.3+, Al.sup.3+, Zn.sup.2+, NH.sub.4.sup.+ or the ammonium ion of an amine compound, selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine, and piperazine,  and/or (P-ii) when —X— is an oxygen atom, —O—, —OR.sup.3 and —OR.sup.4 together and/or —OR.sup.5 and —OR.sup.6 together and/or —OR.sup.3 and —OR.sup.5 together and/or —OR.sup.4 and —OR.sup.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.sup.3 and —OR.sup.4 and/or —R.sup.3 and —OR.sup.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.sup.5 and —OR.sup.6 and/or —OR.sup.4 and —OR.sup.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.sup.1 to R.sup.6 or B.) one of the cycles formed when 1) the substituents R.sup.3-R.sup.6 form acyclic phosphinic or phosphonic acid ester according to (P-ii) or (P-iii), or 2) the substituents R.sup.3-R.sup.6 form a cyclic phosphinic or phosphonic acid anhydride according to (P-ii) or (P-iii), or 3) the substituents R.sup.1 and R.sup.2 form a heterocycle according to (N-ii),  has a first uncharged or negatively charged functional group that has  a) a heteroatom selected from the group consisting of P, O, N, S, I, Cl, Br, F and/or  b) an alkene or alkine group,  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.

2: The composition according to claim 1, wherein at least one of the substituents R.sup.1 to R.sup.6 or any of the cycles formed by the substituents R.sup.1 to R.sup.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 and/or further functional group are selected from the group consisting of —NH.sub.2, —NHR, —NR.sub.2, —OH, —OR, ═O, —SH, —SR, —COOH, —COOR, —OCN, —SiR.sub.xH.sub.y, —I, —Cl, —Br, —F, —N.sub.3, epoxy, lactam, lacton, aziridine, glycolide, oxazoline, ether, alkenylene and alkinylene, 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, preferably by using the flame retardant as a co-monomer in the polymer forming reaction of the polymer material.

5: The composition according to claim 1, wherein R.sup.1 and R.sup.2 are identical substituents.

6: The composition according to claim 1, wherein the first and/or further functional group is an alkenyl or epoxy group.

7: The composition according to claim 1, wherein the dry flame retardant reaches a loss of mass of 10% by weight starting at a temperature of 180° C.

8: The composition according to claim 1, wherein the phosphorus content of the flame retardant is at least 10.0% by weight.

9: The composition according to claim 1, wherein at least one of the groups R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are a cation or H, wherein the cation is Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, B.sup.3+, Al.sup.3+, Zn.sup.2+, NH.sub.4.sup.+ or the ammonium ion of an amine compound, selected from the group consisting of melamine of its condensation products.

10: The composition according to claim 1, wherein the polymer material contains the flame retardant in a quantity of at least 3% by weight and/or in a quantity of not more than 35% by weight, in relation to the entire composition.

11: The composition according to claim 1, wherein the 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.

12: 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, wherein the polymer material is polyester or a polyurethane.

13: A flame retardant as defined in claim 1, wherein the substitutes R.sup.3 to R.sup.6 or the cycles formed by these have the first functional group.

14: A method for producing a flame retardant that comprises the following steps: Provide a mixture of a) at least one phosphonic or phosphinic acid, selected from the group consisting of the compounds of the formulae (V) and (VI) in a reaction vessel, ##STR00109## wherein —X— is an oxygen atom, —O—, or —X— is a single bond, and wherein (P-i) R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are identical or different substituents and are selected from the group consisting of H, linear, branched, or cyclic alkyles, alkenyles and alkinyles, unsubstituted and alkylsubstituted phenyles, multinuclear aromatics having up to 4 nuclei, mononuclear or multinuclear heteroaromatics having up to 4 nuclei, silyles, allyl, alkyl or aryl alcohols, of the following structures (III) and (IV), where n=0 to 100, ##STR00110##  and cations wherein the cation is Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, B.sup.3+, Al.sup.3+, Zn.sup.2+, NH.sub.4.sup.+ or the ammonium ion of an amine bond, selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine, and piperazine,  and/or (P-ii) when —X— is an oxygen atom, —O—, —OR.sup.3 and —OR.sup.4 together and/or —OR.sup.5 and —OR.sup.6 and/or —OR.sup.3 and —OR.sup.5 together and/or —OR.sup.4 and —OR.sup.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.sup.3 and —OR.sup.4 and/or —R.sup.3 and —OR.sup.5 together, including the P atom of the phosphinate group, form a cyclic phosphonic acid ester or a cyclic phosphonic acid anhydride having a ring size of 4-10 atoms and/or —OR.sup.5 and —OR.sup.6 and/or —OR.sup.4 and —OR.sup.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, b) HC(OR.sup.7).sub.3, where R.sup.7=alkyl, aryl or alkenyl, preferably triethoxymethane, c) of an amino compound of the formula (VII), ##STR00111## wherein (N-i) R.sup.1 and R.sup.2 are identical or different substituents and are selected from the group consisting of linear, branched, or cyclic alkyles, alkenyles and alkinyles, unsubstituted and alkyl-substituted phenyles, mononuclear and multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyles, allyl, alkyl, or aryl alcohols, or (N-ii) R.sup.1 and R.sup.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, wherein these nitrogen atoms are preferably substituted on the heterocycle—if it has nitrogen atoms as ring atoms—with H, an alkyl, an aryl, or a methylbisphosphonate group having the following structure (II), ##STR00112##  and wherein on the heterocycle—if it has carbon, phosphorus, or silicon as ring atoms—these atoms can preferably have substituents preferably selected from the group consisting of H, alkyl, aryl, —NH.sub.2, —NHR, —NR.sub.2, —OH, —OR, ═O, —I, —Cl, —Br, F, —Ni, —SH, —SR, —OCN, epoxy, lactam, lacton, aziridin, glycolide, oxazolin, alkenylene, and alkinylene, —SiR.sub.xH.sub.y, where R=alkyl, alkenyl, alkinyl or aryl and x+y=3, Heat the mixture to a temperature in the range from 40-150° C.

15: A method comprising surface treating or coating a substrate with a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt, or a mixture for surface treatment, ##STR00113## wherein (N-i) R.sup.1 and R.sup.2 are identical or different substituents and are selected from the group consisting of linear, branched, or cyclic alkyles, alkenyles and alkinyles, unsubstituted and alkylsubstituted phenyles, mononuclear and multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyles, allyl, alkyl, or aryl alcohols, or (N-ii) R.sup.1 and R.sup.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, wherein these nitrogen atoms are preferably substituted on the heterocycle—if it has nitrogen atoms as ring atoms—with H, an alkyl, an aryl, or a methylbisphosphonate group having the following structure (II), ##STR00114##  and wherein on the heterocycle—if it has carbon, phosphorus, or silicon as ring atoms—these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, —NH.sub.2, —NHR, —NR.sub.2, —OH, —OR, ═O, —I, —Cl, —Br, F, —N.sub.3, —SH, —SR, —OCN, epoxy, lactam, lacton, aziridine, glycolide, oxazoline, alkenylene, and alkinylene, —SiR.sub.xH.sub.y, where R=alkyl, alkenyl, alkinyl or aryl and x+y=3, and wherein —X— is an oxygen atom, —O—, or —X— is a single bond, and wherein (P-i) R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are identical or different substituents and are selected from the group consisting of H, linear, branched, or cyclic alkyles, alkenyles and alkinyles, unsubstituted and alkylsubstituted phenyles, multinuclear aromatics having up to 4 nuclei, mononuclear or multinuclear heteroaromatics having up to 4 nuclei, silyles, allyl, alkyl or aryl alcohols, of the following structures (III) and (IV), where n=0 to 100, ##STR00115##  and cations wherein the cation is Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, B.sup.3+, Al.sup.3+, Zn.sup.2+, NH.sub.4.sup.+ or the ammonium ion of an amine compound, selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine, and piperazine,  and/or (P-ii) when —X— is an oxygen atom, —O—, —OR.sup.3 and —OR.sup.4 together and/or —OR.sup.5 and —OR.sup.6 and/or —OR.sup.3 and —OR.sup.5 together and/or —OR.sup.4 and —OR.sup.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-ii) when —X— is a single bond, —R.sup.3 and —OR.sup.4 and/or —R.sup.3 and —OR.sup.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.sup.5 and —OR.sup.6 and/or —OR.sup.4 and —OR.sup.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,

Description

EXAMPLES

[0136] The invention will now be discussed in detail based on concrete embodiments of flame retardants according to the invention, manufacturing examples for compositions according to the invention, and based on flame retardant examples, and based on the enclosed drawings.

[0137] Concrete Embodiments of Flame Retardant. According to the Invention

[0138] Embodiments with a First Functional Group on the Amino Group

TABLE-US-00001 # [00015] X R.sup.3 R.sup.4 R.sup.5 R.sup.6 1 [00016] —O— H H H H 2 [00017] —O— Ethyl Ethyl Ethyl Ethyl 3 [00018] —O— Butyl Butyl Butyl Butyl 4 [00019] —O— H Na Na Na

[0139] Embodiments with a First and Second Functional Group on the Amino Group

TABLE-US-00002 # [00020] X R.sup.3 R.sup.4 R.sup.5 R.sup.6 5 [00021] —O— H H H H 6 [00022] —O— Ethyl Ethyl Ethyl Ethyl 7 [00023] —O— Butyl Butyl Butyl Butyl 8 [00024] —O— H Na Na Na

[0140] Embodiments with a First Functional Group on One of the Phosphonic Acid Groups

TABLE-US-00003 # R.sup.1 R.sup.2 X [00025] R.sup.5 R.sup.6  9 Ethyl Ethyl Single bond [00026] H H 10 Ethyl Ethyl Single bond [00027] Na Na 11 Ethyl Ethyl Single bond [00028] Methyl Methyl 12 Ethyl Ethyl Single bond [00029] Ethyl Ethyl 13 Ethyl Ethyl Single bond [00030] Butyl Butyl

[0141] Embodiments with a First Functional Group on One of the Phosphonic Acid Groups

TABLE-US-00004 # R.sup.1 R.sup.2 X [00031] R.sup.5 R.sup.6 14 Ethyl Ethyl Single bond [00032] H H 15 Ethyl Ethyl Single bond [00033] Na Na 16 Ethyl Ethyl Single bond [00034] Methyl Methyl 17 Ethyl Ethyl Single bond [00035] Ethyl Ethyl 18 Ethyl Ethyl Single bond [00036] Butyl Butyl

[0142] Embodiments with a First Functional Group on One of the Phosphonic Acid Groups

TABLE-US-00005 # R.sup.1 R.sup.2 X [00037] R.sup.5 R.sup.6 18 Ethyl Ethyl Single bond [00038] H H 19 Ethyl Ethyl Single bond [00039] Na Na 20 Ethyl Ethyl Single bond [00040] Ethyl Ethyl 21 Ethyl Ethyl Single bond [00041] Ethyl Ethyl 22 Ethyl Ethyl Single bond [00042] Butyl Butyl

[0143] Embodiments with a First Functional Group on One of the Phosphonic Acid Groups

TABLE-US-00006 # R.sup.1 R.sup.2 X [00043] R.sup.5 R.sup.6 23 Ethyl Ethyl Single bond [00044] H H 24 Ethyl Ethyl Single bond [00045] Na Na 25 Ethyl Ethyl Single bond [00046] Ethyl Ethyl 26 Ethyl Ethyl Single bond [00047] Butyl Butyl

[0144] Embodiments with a First and Second Functional Group on the Phosphonic Acid Groups

TABLE-US-00007 # R.sup.1 R.sup.2 X [00048] R.sup.5 R.sup.6 27 Ethyl Ethyl Single bond [00049] [00050] H 28 Ethyl Ethyl Single bond [00051] [00052] Na 29 Ethyl Ethyl Single bond [00053] [00054] Ethyl 30 Ethyl Ethyl Single bond [00055] [00056] Butyl

[0145] Embodiments with a First Functional Group on One of the Phosphonic Acid Groups

TABLE-US-00008 # R.sup.1 R.sup.2 X [00057] R.sup.5 5 31 Ethyl Ethyl Single bond [00058] [00059] 10 32 Ethyl Ethyl Single bond [00060] [00061] 15 33 Ethyl Ethyl Single bond [00062] [00063] 20 34 Ethyl Ethyl Single bond [00064] [00065] 25

[0146] Embodiments with First Cyclic Functional Aroup

TABLE-US-00009 # R.sup.1 R.sup.2 X [00066] R.sup.3 35 Ethyl Ethyl Single bond [00067] H 36 Ethyl Ethyl Single bond [00068] Na 37 Ethyl Ethyl Single bond [00069] Ethyl 38 Ethyl Ethyl Single bond [00070] Butyl

[0147] Embodiments with First Cyclic Functional Group

TABLE-US-00010 # R.sup.1 R.sup.2 X [00071] R.sup.3 39 Ethyl Ethyl Single bond [00072] H 40 Ethyl Ethyl Single bond [00073] Na 41 Ethyl Ethyl Single bond [00074] Ethyl 42 Ethyl Ethyl Single bond [00075] Butyl

[0148] Embodiments with First Cyclic Functional Group

TABLE-US-00011 # R.sup.1 R.sup.2 X [00076] R.sup.3 43 Ethyl Ethyl Single bond [00077] H 44 Ethyl Ethyl Single bond [00078] Na 45 Ethyl Ethyl Single bond [00079] Ethyl 46 Ethyl Ethyl Single bond [00080] Butyl

[0149] Embodiments with Morpholine, MOMP

TABLE-US-00012 # [00081] X R.sup.3 R.sup.4 R.sup.5 R.sup.6 47 [00082] —O— H H [00083] H 48 [00084] —O— Ethyl Ethyl [00085] Ethyl 49 [00086] —O— Butyl Butyl [00087] Butyl 50 [00088] —O— H Na [00089] Na

[0150] Embodiments with Piperazine, PIMP

TABLE-US-00013 # [00090] X R.sup.3 R.sup.4 R.sup.5 R.sup.6 51 [00091] —O— H H [00092] H 52 [00093] —O— Ethyl Ethyl [00094] Ethyl 53 [00095] —O— Butyl Butyl [00096] Butyl 54 [00097] —O— H Na [00098] Na

[0151] Production Examples for Compositions According to the Invention

[0152] Input Substances:

TABLE-US-00014 Name Manufacturer Purity/M.sub.n CAS 4-Formylmorpholine Alfa Aesar    99% 4394-85-8 N,N-Dimethylformamide Merck KGaA   ≥99% 68-12-2 Phosphonic acid Alfa Aesar   99+% 4394-85-8 Acetic acid anhydride Merck KGaA   ≥98% 108-24-7 Methylenediphenylisocyanate Sigma Aldrich M.sub.n~340 9016-87-9 (MDI) Polyol Sigma Aldrich M.sub.n~4000 9082-00-2 Pentan Sigma Aldrich water-free, 109-66-0 ≥99 Ethyleneglycol Sigma Aldrich water-free, 107-21-1 ≥99.8 Triethoxymethane Alfa Aesar    98% 122-51-0 Morpholine Merck ≥99.0% 110-91-8 4-Piperidone-Ethyleneketal Sigma Aldrich   98% 1 77-11-7 Vinyl-bromide in THF (1 M) Sigma Aldrich 593-60-2 4-Hydroxypiperidine Merck    98% 5382-16-1 4-Methylene-Piperidine- Advanced    95% 144230-50-2 hydrochloride Chemblocks Inc Triethylamine Sigma Aldrich    99% 121-44-8 Morpholine Merck ≥99.0% 110-91-8 Diethylphosphit Acros Organics    98% 762-04-9 Vinylbromide Sigma Aldrich    98% 593-60-2

[0153] Further Flame Retardants: [0154] Budit 240: phosphorus-based, partially cross-linked polyacrylate, produced according to example 1 of WO 2014/124933 [0155] Budit 315: Melamincyanurate from Chemische Fabrik Budenheim KG [0156] Budit 342: Melaminepolyphosphate from Chemische Fabrik Budenheim KG [0157] Budit 667: intumescent flame retardant system from Chemische Fabrik Budenheim KG based on ammoniumpolyphosphate [0158] TCPP: Tris(2-chlorisopropyl)phosphate TCPP of Sigma Aldrich (GAS: 13674-84-5) [0159] OP 550: Phosphorus-based polyole Exolit OP 550 of Clariant AG (CAS: 184538-58-7)

[0160] Measurement Methods:

[0161] Dynamic difference calorimetry (DSC)—measurements were taken with a device for simultaneous thermogravimetry—Dynamic difference calorimetry (STA/TG-DSC), Model STA409 PC/3/H Luxx, Netzsch Gerätebau GmbH, in the range from 25 to 500° C. under nitrogen atmosphere with a heating rate of 10K/min. The initial sample weights were approx. 15 mg. The software NETZSCH Proteus was used for analysis.

[0162] Thermogravimetric analyses (TAG) were conducted with a device for simultaneous thermogravimetry—Dynamic difference calorimetry (STA/TG-DSC), Model STA409 PC/3/H Luxx, Netzsch GerAtebau GmbH, in the range from 25 to 800° C. under nitrogen atmosphere with a heating rate of 10K/min. The initial sample weights were approx. 12-15 mg. The software NETZSCH Proteus was used to analyze the TGA graphs.

[0163] Production Examples for Compositions According to the Invention

Example 1: Synthesis of Morpholin-methylaminodiphosphonic acid (MOMP-H.SUB.4.)

[0164] 0.1 mol 4-Formylmorpholine were measured into a 500 ml round flask and mixed with 0.2 mol phosphonic acid and 30 ml acetic acid anhydride. The reaction solution was agitated at 65° C. for 90 minutes. The generated acetic acid and excess water were then removed on the rotation evaporator under reduced pressure of ˜30 mbar. The residual was then removed from the remaining solvent in the drying cabinet at 85° C., 4 hrs.

Example 2: Synthesis of Piperazin-di(methylaminodiphosphonic acid) (PIMP-H.SUB.4.)

[0165] 0.28 mol phosphonic acid was dissolved in 31 ml fully de-ionized water in a 250 ml round flask while stirring. A solution of 0.07 mol Diformylpiperazine was dripped into 30 ml fully deionized water over a span of 15 min. A temperature increase of a few degrees was observed during the addition. After the addition ended, the reaction mixture was stirred for 3 hrs. under backflow. After the solution cooled, excess water was removed on the rotational evaporator. A saturated piperazine solution was dripped into the liquid distillation residue. White-amorphous precipitation formed during heating.

Example 3: Synthesis of Dknethyl-methylaminodlphosphonic acid (DAMP-H.SUB.4.)

[0166] 0.9 mol Dimethylformamide were measured into a 500 ml round flask and mixed with 1.8 mol phosphonic acid and 225 ml acetic acid anhydride. The reaction solution was stirred at 90° C. for 90 minutes. The generated acetic acid and excess water were then removed on the rotation evaporator under reduced pressure of ˜300 mbar. The residual was then removed from the remaining solvent in the drying cabinet at 85° C., 4 hrs.

Example 4: Synthesis of an Aqueous Solution of the trianatrium salt of Morpholin-methylaminodiphosphonic acid (MOMP—H—Na.SUB.3.)

[0167] 0.289 mmol Morpholin-methylaminodiphosphonic acid (MOMP-H.sub.4) were dissolved in 50 ml fully de-ionized water, followed by adding 0.867 mmol NaOH. A pH value of ˜9 was obtained for the solution.

Example 5: Synthesis of Morpholin-methylaminodlphosphonic tetreethylester (MOMP-H.SUB.4.)

[0168] MOMP-Et.sub.4 was rendered by measuring 0.1 mol morpholine into the reactor while stirring. 0.1 mol triethoxymethane are then dripped in. 0.2 mol diethylphosphite are then added. The mixture is heated to 120° C. and stirred 4 hrs. at this temperature. After the reaction ends, the product is cleaned by vacuum distillation at 50 mbar and 150° C.

[0169] In a preferred embodiment, all substituents R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are cations or organic residuals, particularly preferably ethyl, since correspondingly substituted compounds can act as catalysts for the polyurethane foam synthesis. Use of such compounds is particularly advantageous since these accelerate the synthesis and also improve the flame-retarding properties of the finished polymer. Compounds with P—OH groups, such as MOMP-H.sub.4, do not exhibit a corresponding catalytic effect, probably because these are present in the form of a dipolar ion (PO.sup.−/NH.sup.+) whose quaternary amino group does not have a catalytic property.

[0170] The so-called start time until foaming is significantly reduced when correspondingly substituted compounds are used compared to compounds with P—OH group, such as MOMP-H.sub.4, as will be shown based on the following tests.

[0171] General methodology: Polyol (22.5 g) is mixed with the catalyst (Ethylene glycol, 1.05 g) Pentan (4.5 g) and the respective flame retardant at 1000 R/min. The isocyanate (MDI, 60.0 g) is added with the disperser switched off; the mixture is then stirred 10 seconds at 1500 R/min and then promptly refilled.

TABLE-US-00015 Batch loading Time [s] Flame retardant [php]* to foaming without 0 15 MOMP-H.sub.4 7.5 15 MOMP-H.sub.4 5.0 10 MOMP-H.sub.4 2.5 5 MOMP-Et.sub.4 10 0-1 Exolit OP 550 7.5 15 Exolit OP 550 2.5 15 TCPP 7.5 10 TCPP 2.5 10 *php-parts per hundred parts of polyol

Example 6: Synthesis of Morpholin-methylaminodi-DOPO (MOM-DOPO.SUB.2.)

[0172] ##STR00099##

TABLE-US-00016 Name Smp. Sdp. M DOPO (Metadynea ~120° C. ~400° C. 216.18 g/mol DOP11 S25) 4-FM (AlfaAesar > 98%)    20° C.   240° C. 115.13 g/mol Ac.sub.2O (Merck > 98%)   −73° C.   139° C. 102.09 g/mol MOM-DOPO.sub.2 n.a. n.a. 529.47 g/mol Water    0° C.   100° C. 18.02 g/mol Acetic acid    17° C.   118° C. 60.05 g/mol

[0173] This reaction is a condensation reaction that generates the product MOM-DOPO.sub.2 from the formyl function on the 4-Formylmorpholine (4-FM) and the P—H groups of the DOPO molecules, with H.sub.2O splitting. 40 g DOPO are dissolved in 100 ml acetic acid anhydride (Ac.sub.2O) while stirring into a 250 ml beaker, followed by heating the mixture to 120° C. 10 g 4-FM are added when the temperature is reached. The solution is neutralized after 5 hours with 80 ml water, followed by setting exterior tempering. A white solid precipitates after cooling, which is filtered off and washed with water. Acetic acid is generated as a further byproduct.

Example 7: Synthesis of Morpholin-methylaminodlphosphonic acid Zn salt (MOMP-H.SUB.2.)

[0174] The Zn salt (1:1) is rendered by dispersing 50.0 g (0.191 mol) MOMP in 500 g H.sub.2O, followed by cutting with 14.6 g ZnO (0.191 mol). The reaction mixture is heated to 95° C. and stirred 4 hrs. at this temperature. The batch is then cooled to below 50° C., followed by separating the solids from the mother liquor. The filter cake is dried at 120° C. in circulating air.

TABLE-US-00017 Name Manufacturer Purity/M.sub.n CAS MOMP see example 1 ZnO Alfa Aesar min. 99.0% 1314-13-2 H.sub.2O dest.

Example 8: Synthesis of Piperazin-dl(methylaminodlphosphonic acid) (PIMP-H.SUB.4.)

[0175]

TABLE-US-00018 Name Manufacturer Purity CAS Molar Mass 1,4-Diformylpiperazine Alfa Aesar 98+% 4164-39-0 142.16 g/mol Acetic acid anhydride VWR AnalaR NORMAPU 108-24-7 102.09 g/mol Phosphorous acid Alfa Aesar 97% 13598-3-2 82.0 g/mol H.sub.2O dest. NaOH solution 50% 1310-73-2 39.997 g/mol Sulfuric acid Merck 95-97% 7664-93-9 98.08 g/mol

[0176] 0.1 mol 1,4-Diformylpiperazine and 0.1 mol acetic acid anhydride are filled into the reactor and mixed. The mixture is heated to 120° C. 0.4 mol phosphorous acid are dissolved separately in 0.3 mol acetic acid anhydride. This solution is then dripped into the reactor. Finally, a further 0.5 mol acetic acid anhydride are added, followed by heating the batch to 135° C. 2.1 mol water are dripped in after a 30 minute reaction time. The batch is cooled to room temperature after an additional 40 min reaction time. 70 ml sodiumhydroxide solution are then added. The product is separated from the mother liquor and dissolved in water. The solution is then reprecipitated in sulfuric acid, followed by filtering off, washing, and drying the product.

Example 9: Synthesis of diethylphosphite

[0177] Phosphonic acid (29.7 g, 0.36 mol) and triethoxymethane (107.3 g, 0.72 mol) are mixed in a 500 ml three-necked flask with distillation apparatus, followed by heating to 90° C. while stirring. After 45 minutes, the temperature is increased to 135° C. to initiate boiling (gas phase temperature 73° C.) and to obtain a first fraction of ethanol and ethylformiate. After boiling stops, vacuum (30 mbar) is applied to obtain a second fraction. The associated product is diethylphosphite. 35.0 g of the colorless, low-odor liquid are obtained.

Example 10: Synthesis of 4-Hydroxy-1-(methylaminodlphosphonic acid) Piperidin (“OH-PIDMP-H.SUB.4.”)

[0178] ##STR00100##

[0179] “OH-PIDMP-Et.sub.4” is rendered by adding 4-Hydroxypiperidin (0.1 mol) to a 250 ml flask and stirring. Triethoxymethane (0.1 mol) is dripped in. 0.2 mol diethylphosphite are then added. The mixture is heated to 120° C., stirred 4 hrs. at this temperature, followed by cleaning the product “OH-PIDMP-Et.sub.4” by vacuum distillation at 50 mbar and 150° C.

##STR00101##

[0180] The product is then blended with a 5-fold excess of 1 N HCl, wherein minor heating can be observed. The generated ethanol is distilled off, thus obtaining the product “OH-PIDMP-H.sub.4” with a yield of 89%. The melting point is 250° C.

Example 11: Synthesis of 4-Methylene-1-(methylaminodlphosphonic acidtetraethylester)-Piperidin (“4-Methylene-PIDMP-Et.SUB.4.”)

[0181] ##STR00102##

[0182] “4-Methylen-PIDMP-Et.sub.4” is rendered by filling 4-Methylidenpiperidin-hydrochloride (0.05 mol) and triethylamine (0.1 mol) into a 250 ml flask and stirring. Triethoxymethane (0.12 mol) is dripped in. This if followed by adding diethylphosphite (0.31 mol). The mixture is heated to 140° C. and stirred 6 hrs. at this temperature. After cooling to room temperature, diethylether (125 ml) is added, the mixture is neutralized with sodiumhydroxide solution (0.5 N, 50 ml), the phases are separated and the organic phase is washed with 250 ml water. The organic phase is processed by distillation, wherein the product has a boiling point of 180° C. at 2 mmbar. The yield is 58%.

Example 12: Synthesis of 4-Hydroxy-4-Vinyl-1-(methylaminodlphosphonic acid tetra-ethylester)-Piperidin (“OH-Vinyl-PIDMP-Et.SUB.4.”)

[0183] ##STR00103##

[0184] “OH-Vinyl-PIDMP-Et.sub.4” is rendered by filling 4-Piperidon-Ethylenketal (0.1 mol) into a 250 ml flask and stirring. Triethoxymethane (0.1 mol) is dripped in. 0.2 mol diethylphosphite are then added. The mixture is heated to 120° C., stirred 4 hrs., followed by cleaning the product “Ketal-PIDMP-Et” by vacuum distillation at 50 mbar and 150° C.

##STR00104##

[0185] “Ketal-PIDMP-Et.sub.4” is cut with a 5-fold molar excess of 80% acetic acid and stirred 2 hrs. at 80° C. The generated ethylene glycol is distilled off and the interim product “Keton-PIDMP-Et.sub.4” is cleaned by vacuum distillation at 50 mbar and 150° C.

##STR00105##

[0186] “OH-Vinyl-PIDMP-Et.sub.4” is rendered by filling THF (absolute) as solvent into a water-free apparatus, followed by producing the Grignard reagent therein (c=1.5 molar). Magnesium chips are then added to the THF, while continuously dripping in vinyl bromide (1.2 mmol). The “Keton-PIDMP-Et.sub.4” (1 mmol) is continuously dripped in. After the reaction ends (evidenced by reduced boiling, total reaction time: ˜2 hrs.), the reaction mixture is hydrolized with cooled 1N HCl(aq). The mixture is processed by separating the aqueous phase and removing the solvent from the organic phase by distillation. The melting point of the obtained “OH-Vinyl-PIDMP-Et.sub.4” is 239° C. The reaction yield is 85%.

[0187] Flame Retardant Examples:

[0188] Compositions

[0189] The UL94 test was performed on IEC/DIN EN 60695-11-10 standard-compliant test specimens to verify the flame retarding properties and to classify the flame retardant compositions according to the invention in various polymers.

[0190] UL94-V Test

[0191] For each measurement, respectively 5 test specimens were clamped in a vertical position, followed by holding the test specimen to the open end of a Bunsen burner flame. The burn time and also the dropping of burning particles were evaluated with a cotton pad arranged under the test specimen. The tests and exposure to a 2 cm high Bunsen burner flame were accurately performed as specified by Underwriter Laboratories, Standard UL94.

[0192] The classification into fire protection classes V-0 to V-2 are cited as results. V-0 in this case means that the total burn time of 5 tested test specimens was less than 50 seconds and that the cotton pad was not set aflame by glimmering or burning droplets of the test specimen. The classification V-1 means that the total burn time of 5 tested test specimens was more than 50 seconds but less than 250 seconds and that the cotton pad was likewise not set aflame. V-2 in this case means that the total burn time of 5 tested test specimens was less than 250 seconds but that the cotton pad was set aflame by glimmering or burning droplets in at least one of the 5 tests. The abbreviation NC means “not classifiable” and indicates that a total burn time of more than 250 seconds was measured. In many cases of non-classiflability, the test specimen burned completely.

[0193] UL94-HB Test

[0194] For each measurement, respectively at least 3 test specimens were clamped in a horizontal position, followed by holding the test specimen to the open end of a Bunsen burner flame. This involved evaluating the burn rate and the total burn distance. The tests and exposure to a 2 cm high Bunsen burner flame were accurately performed as specified by Underwriter Laboratories, Standard UL94.

[0195] The classification into fire protection class HB is cited as the result. The “HB” classification means that the burn rate between two markers, the first at a 25 mm distance from the flame-facing end, the second at a 100 mm distance from the flame-facing end, was less than 40 mm/min. The flame front also did not exceed the 100 mm marker The “NC” classification means “Not Classifiable” and indicated that the burn rate over a distance of 75 mm was >40 mm/min or the total burn distance was >100 mm.

[0196] L*a*b* Values

[0197] The L*a*b* values were determined with an UltraScan VIS-2 Spectralphotometer equipped with the UltraScanVIS Sensor from HunterLab. The samples were for this purpose filled into a glass cuvette, followed by impacting the cuvette or densifying the sample to create a homogeneous surface on the cuvette side toward the measurement opening. The associated Easy Match QC 4.64 b software uses the “USVIS 1145” Sensor and “RSIN Mode” setting to calculate the L*a*b* values.

[0198] The method is compliant with EN ISO 11664-4 in its currently valid version.

Example 13: Flame-Retardant Properties of MOMP-H.SUB.4 .in Polypropylene

[0199] Polymers

[0200] The following polymer materials were used in the examples to follow to produce the flame-retarding compositions:

[0201] Polypropylene (PP) HD120 MO from Borealis AG

[0202] A twin screw extruder, model Process 11, Thermo Fisher Scientific Inc., was used to produce a granulate with approximate grain size 3×1×1 mm at extrusion conditions typical for polypropylene. The extrusion process was run at an approximate throughput of 5-7 kg/h and at a screw speed of 450-500 rpm and a temperature of the extrusion zone of 190-220° C. High-quality UL94-compliant test specimens were then obtained by hot pressing. The thickness of the test specimens was 1.6 and 3.2 mm respectively. The phosphonate produced according to example 1 was then incorporated into the polymer material during the extrusion process.

TABLE-US-00019 TABLE 1 Thick- PP ness MOMP Budit Budit # [%] [mm] [%] 667 240 UL94 t.sub.1 t.sub.2 t.sub.ges 0 100 1.6 0 — — N.C. 376* —* 376 1 75 1.6 25 — — N.C. 95 70 165 2 72.5 1.6 27.5 — — V-2 9 54 63 3 75 3.2 25 — — V-0. 4 6 10 4 72.5 3.2 27.5 — — V-0 4 4 8 5 75 3.2 — 25 — V-0 5 5 10 6 75 1.6 — — 25 N.C 231 34 265 7 72.5 1.6 — — 27.5 N.C 227 28 255

Example 14: Flame-Retardant Properties of MOMP-H.SUB.4 .in Polyurethane (PU)

[0203] The flame-retardant compositions were produced by converting the following components together in a foaming reaction:

[0204] Polyol: 22.5 g

[0205] Catalyst (ethylene glycol): 1.05 g

[0206] Pentan: 4.5 g

[0207] Isocyanate (MDI): 60 g

[0208] The flame retardant according to the invention was added to the polyol component prior to the reaction. The mass ratios of the flame retardant cited in the following table refer to the sum of the masses of polyol, catalyst, flame retardant, and isocyanate.

TABLE-US-00020 PU Flame retardant Batch load # [%] [%] [%] UL94-HB t.sub.ges 0 100 — — N.C. 50 1 98.2 MOMP-H.sub.4 1.8 HB 7 2 98.2 MOMP-2K.sup.# 1.8 N.C. 30 3 91.8 MOMP-2K.sup.# 8.2 N.C. 20 4 98.2 DAMP-H.sub.4 1.8 HB 4 5 98.2 TCPP 1.8 N.C. 26 6 97.1 OP 550 2.9 HB 32 7 97.4 MOMP-Et.sub.4 2.6 HB 4  8** 97.4 MOMP-Et.sub.4 2.6 HB 6 .sup.#double potassium salt of MOMP-H.sub.4 **w/o catalyst

Example 15: Flame-Retardant Properties of MOMP-H.SUB.4 .in Thermoplastic Polyurethane (PU)

[0209] The following polymer materials were used in the examples to follow to produce the flame-retarding compositions:

[0210] Thermoplastic Polyurethane (TPU) Elastollan 1185 A from BASF SE

[0211] A twin screw extruder, model Process 11, Thermo Fisher Scientific Inc., was used to produce a granulate with approximate grain size 3×1×1 mm at extrusion conditions typical for TPU. The extrusion process was run at an approximate throughput of 5 kg/h and at a screw speed of 300 rpm and a temperature of the extrusion zone of 205° C. High-quality UL94-compliant test specimens were then obtained by hot pressing. The thickness of the test specimens was 0.8 mm. The phosphonate produced according to example 1 was then incorporated into the polymer material during the extrusion process.

TABLE-US-00021 Budit TPU Budit Budit 240 MOMP Batch # [%] 315 [%] 342 [%] [%] [%] load [%] UL94 t.sub.1 t.sub.2 t.sub.ges Info 0 100 — — — — 0 N.C. 323.sup.− —.sup.− 323 butc * 1 90 — 5 — 5 10 V-2 4 2 6 4/5 ditc.sup.# 2 90 5 — — 5 10 V-0 2 4 6 — 3 90 — — — 10 10 V-0 9 5 14 — 4 90 10 — — — 10 V-0 3 5 8 — 5 90 — 10 — — 10 V-2 11 5 16 5/5 ditc.sup.# 6 90 5 — 5 — 10 V-2 3 1 4 5/5 ditc.sup.# *butc = test sample burns down to the clamp .sup.#ditc = falling droplets set cotton aflame .sup.−second flame exposure not possible because test specimen already burned off after first flame exposure

Example 16: Flame-Retardant Properties of MOMP-H.SUB.2.Zn in Thermoplastic Polyamide (PA)

[0212] The following materials were used in the examples to follow to produce the flame-retarding compositions:

[0213] Polyamide 6: Ultramid B3S (BASF)

[0214] Glass fibers (GF) for PA: CS7928 (Lanxess)

[0215] A twin screw extruder, model Process 11, Thermo Fisher Scientific Inc., was used to produce a granulate with approximate grain size 3×1×1 mm at extrusion conditions typical for PA6. The extrusion process was run at an approximate throughput of 5 kg/h and at a screw speed of 300 rpm and a temperature of the extrusion zone of 280° C. High-quality UL94-compliant test specimens were then obtained by hot pressing. The thickness of the test specimens was 0.8 mm. The phosphonate produced according to example 7 (MOMP-H.sub.2Zn) was then incorporated into the polymer material during the extrusion process.

TABLE-US-00022 PA6 FG Budit Exolit** MOMP Budit UL9 t.sub.1 t.sub.2 t.sub.ges # [%] [%] 611 [%] [%] H.sub.2Zn 341 [%] 4-V [s] [s] [s] Info 0 44.8 30 23 2.2 V0 8 10 18 1 55 30 15 N.C. 243 ~ butc 2 50 30 20 V0 12 5 17 3 45 30 25 V0 6 2 8 4 45 30 17.5 7.5 V0 9 9 18 *butc = test sample burns down to the clamp **Exolit OP 1230 ~second flame exposure not possible because test specimen already burned off after first flame exposure

Example 17: Flame-retarding and Transparency Properties of MOMP-Et.SUB.4 .in a Thermoplastic Polyurethane Coating

[0216] A polyurethane resin top-coat Goylake A-1219-9 from Irurena Group was cut with MOMP-Et.sub.4 and mixed while stirring vigorously. The ratio of MOMP-Et.sub.4 in the total mass (250 g) consisting of the mass of MOMP-Et.sub.4 and the mass of the polyurethane resin was 5% by weight (recipe A) or 10% by weight (recipe B). In relation to this total mass, respectively 10% by weight of the curing catalyst C-212 from Irurena Group were added, followed by mixing the mixture while stirring vigorously.

[0217] The transparent mixtures were then applied onto a commercially available chipboard using a 500 μm scraper, followed by drying the panel at 80° C.

[0218] The subsequent Epiradiator fire test according to NF P 92-501 resulted in an M3 classification, both with recipe A and also with recipe B.

[0219] Transparency Measurement

[0220] In order to verify the transparency of recipes A and B, the recipes were each applied as a coating using a 500 μm scraper, in each case on a white and a black substrate. The L*a*b values were then determined for each substrate for respectively two samples with coating (tests No. 1 and 2) and for respectively two control samples (tests No. 3 and 4) without coating.

[0221] As shown in the tables below, coatings with recipe A and B only cause negligible changes of the values in the L*a*b color space, e.g. the coating have high transparency and either do not or only immaterially impact the appearance of the substrate. The flame retardants according to the invention are therefore particularly suited for use in transparent coatings.

[0222] Recipe A

[0223] Black Substrate

TABLE-US-00023 # Coating L* a* b* 1 + 10.2 −0.5 −1.3 2 + 9.1 −0.5 −1.3 3 − 8.2 −0.3 −1.4 4 − 8.1 −0.4 −1.2

[0224] White Substrate

TABLE-US-00024 # Coating L* a* b* 1 + 90.8 −0.5 1.6 2 + 90 6 −0.5 1.7 3 − 91.2 −0.8 1.5 4 − 91.1 −0.9 1.5

[0225] Recipe B

[0226] Black Substrate

TABLE-US-00025 # Coating L* a* b* 1 + 9.0 −0.4 −1.4 2 + 9.0 −0.4 −1.5 3 − 8.6 −0.4 −1.3 4 − 8.4 −0.3 −1.3

[0227] White Substrate

TABLE-US-00026 # Coating L* a* b* 1 + 90.8 −0.6 2 2 + 90.7 −0.4 1.9 3 − 91.1 −0.9 1.6 4 − 91.2 −0.8 1.4

DESCRIPTION OF FIGURES

[0228] The enclosed figures represent thermogravimetric measurements; they show in:

[0229] FIG. 1: Difference calorimetric measurement of DAMP-H4

[0230] FIG. 2: Thermogravimetric measurement of DAMP-H4

[0231] FIG. 3: Difference calorimetric measurement of MOMP-H4

[0232] FIG. 4: Thermogravimetric measurement of MOMP-H4

[0233] FIG. 5: Difference calorimetric measurement of ATMP

[0234] FIG. 6: Thermogravimetric measurement of ATMP

[0235] FIG. 7: Difference calorimetric measurement of MOMP-Et4

[0236] FIG. 8: Thermogravimetric measurement of MOMP-Et4

[0237] FIG. 9: Difference calorimetric measurement of MOMP-DOPO2

[0238] FIG. 10: Thermogravimetric measurement of MOM-DOPO2

[0239] FIG. 11: Difference calorimetric measurement of MOMP-H2Zn

[0240] FIG. 12: Thermogravimetric measurement of MOMP-H2Zn

[0241] FIG. 13: Difference calorimetric measurement of PIMP

[0242] FIG. 14: Thermogravimetric measurement of PIMP

TABLE-US-00027 1% Weight 2% Weight Residual Mass Material Loss Loss at 500° C. MOMP-H.sub.4 251.7° C. 276.9° C. 64.29% DAMP-H.sub.4 244.5° C. 273.1° C. 71.41% ATMP-H.sub.4 176.4° C. 193.9° C. 72.43% MOMP-Et.sub.4 101.7° C. 117.1° C. 19.58% MOM-DOPO.sub.2 305.5° C. 318.9° C.  7.50% MOMP-H.sub.2Zn 375.0° C. 382.3° C. 78.75% PIMP-H.sub.4 199.3° C. 245.4° C. 71.63%