Ethylene diphosphinic acids
Abstract
Ethylenediphosphinic acids and their salts of the general formula (I) in which A represents CR 5 R 6 -OH, AP (O) (OX) -CR 1 R 2 -CR 3 R 4 -P (O) (OX) - A (I) R 1, R 2, R 3, R 4, R 5 and R 6 are the same or different and mean, independently of each other, H, C1-C20 alkyl, C6-C20 aryl and / or aralkyl of C6-C20 and X represents H, an alkali metal, an element of the second major and secondary group, an element of the third major and secondary group, an element of the fourth major and secondary group, an element of the fifth major and secondary group, an element of the sixth secondary group, an element of the seventh secondary group, an element of the eighth secondary group and / or a nitrogen base.
Term
1 yearto projected expiry
Projected expiry 6 October 2027, counted from filing; an application has no term until it is granted.
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11 claims: 3 independent, 8 dependent
- 1REIVINDICACIONES 1. �?cidos etilendifosfínicos y sus sales de la fórmula general (I) A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A (I) en la que A representa CR5R6-OH, R1, R2, R3, R4, R5 y R6 son iguales o diferentes y significan, independientemente unos de otros, H, alquilo de C1-C20, arilo de C6-C20 y/o aralquilo de C6-C20 y X representa H, un metal alcalino, un elemento del segundo grupo principal y secundario, un elemento del tercer grupo principal y secundario, un elemento del cuarto grupo principal y secundario, un elemento del quinto grupo principal y secundario, un elemento del sexto grupo secundario, un elemento del séptimo grupo secundario, un elemento del octavo grupo secundario y/o una base nitrogenada.
- 2�?cidos etilendifosfínicos y sus sales de acuerdo con la reivindicación 1, caracterizados porque R1, R2, R3, R4, R5 y R6 son iguales o diferentes y significan, independientemente unos de otros, H, metilo, etilo, n-propilo, i-propilo, nbutilo, terc.-butilo, n-pentilo y/o fenilo.
- 3Procedimiento (1) para la preparación de ácidos etilendifosfínicos y de sus sales de la fórmula general (I) A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A (I) en la que A representa CR5R6-OH, R1, R2, R3, R4, R5 y R6 son iguales o diferentes y significan, independientemente unos de otros, H, alquilo de C1-C20, arilo de C6-C20 y/o aralquilo de C6-C20 y X significa H, un metal alcalino, caracterizado porque a) se hace reaccionar un aducto del ácido monofosfínico de la fórmula (II) H-P(O)(OX)-A (II) con acetileno o con un compuesto de acetileno y b) facultativamente se separan los ácidos etilendifosfínicos obtenidos del tipo A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A con respecto de los productos secundarios.
- 4Procedimiento (2) para la preparación de sales de ácidos etilen-bis-(hidroxialquilfosfínicos) o de sales de ácidos etilendifosfínicos del tipo A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A en el que A, R1, R2, R3, R4, R5 y R6 tienen los mismos significados que en la reivindicación 1 y X representa un metal alcalino, un elemento del segundo grupo principal y secundario, un elemento del tercer grupo principal y secundario, un elemento del cuarto grupo principal y secundario, un elemento del quinto grupo principal y secundario, un elemento del sexto grupo secundario, un elemento del séptimo grupo secundario, un elemento del octavo grupo secundario y/o una base nitrogenada, caracterizado porque un ácido etilen-bis-(hidroxialquilfosfínico) o un ácido etilendifosfínico del tipo A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A en el que A, R1, R2, R3, R4, R5 y R6 tienen los mismos significados que en la reivindicación 1 y X significa H, se hace reaccionar en el seno de un sistema de disolventes con un partícipe I en la reacción, en cuyo caso se trata de un compuesto de un metal alcalino, de un elemento del segundo grupo principal y secundario, de un elemento del tercer grupo principal y secundario, de un elemento del cuarto grupo principal y secundario, de un elemento del quinto grupo principal y secundario, de un elemento del sexto grupo secundario, de un elemento del séptimo grupo secundario, de un elemento del octavo grupo secundario y/o una base nitrogenada,
- 5Procedimiento (3) para la preparación de sales de ácidos etilen-bis-(hidroxialquilfosfínicos) o de sales de ácidos etilendifosfínicos del tipo A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A en el que A, R1, R2, R3, R4, R5 y R6 tienen los mismos significados que en la reivindicación 1 y X significa un elemento del segundo grupo principal y secundario, un elemento del tercer grupo principal y secundario, un elemento del cuarto grupo principal y secundario, un elemento del quinto grupo principal y secundario, un elemento del sexto grupo secundario, un elemento del séptimo grupo secundario, un elemento del octavo grupo secundario y/o una base nitrogenada, caracterizado porque un ácido etilen-bis-(hidroxialquilfosfínico) o un ácido etilendifosfínico del tipo A-P(O)(OX)-CR1R2-CR3R4-P(O)(OX)-A en el que A, R1, R2, R3, R4, R5 y R6 tienen los mismos significados que en la reivindicación 1 y X significa un metal alcalino, se hace reaccionar en el seno de un sistema de disolventes con un partícipe II en la reacción para dar otra sal metálica (una sal de un metal no alcalino).
- 6Procedimiento de acuerdo con la reivindicación 5, caracterizado porque en el caso del partícipe en la reacción II se trata de boratos, carbonatos, hidroxocarbonatos, hidroxocarbonatos hidratos, hidroxocarbonatos mixtos, hidroxocarbonatos mixtos hidratos, fosfatos, sulfatos, sulfatos hidratos, hidroxosulfatos hidratos, hidrógenosulfatos mixtos hidratos, oxisulfatos, acetatos, nitratos, fluoruros, fluoruros hidratos, cloruros, cloruros hidratos, oxicloruros, bromuros, yoduros, yoduros hidratos, derivados de ácidos carboxílicos y/o alcóxidos.
- 7Utilización de ácidos etilendifosfínicos de acuerdo con la reivindicación 1 o 2 como agentes ignifugantes, en particular como agentes ignifugantes para barnices transparentes y para revestimientos intumescentes, como agentes ignifugantes para maderas y otros productos que contienen celulosas, como agentes ignifugantes reactivos y/o no reactivos para polímeros, para la producción de masas de moldeo poliméricas ignifugadas, para la producción de cuerpos moldeados poliméricos ignifugados y/o para el apresto ininflamable de poliésteres y de tejidos hechos puramente de celulosa y de tejidos mixtos mediante impregnación.
- 8Utilización de ácidos etilendifosfínicos de acuerdo con la reivindicación 1 o 2 como agentes aglutinantes para masas de fundición y arenas de moldeo;como agentes reticulantes o respectivamente aceleradores en el caso del endurecimiento de resinas epoxídicas, poliuretanos y resinas de poliésteres insaturados;como agentes estabilizadores de polímeros, tales como agentes estabilizadores para la protección frente a la luz, agentes captadores de radicales y/o agentes termoestabilizadores para tejidos de algodón, fibras poliméricas y materiales sintéticos;como agentes fitoprotectores, tales como un agente regulador del crecimiento de plantas, como un herbicida, plaguicida o fungicida;como agentes secuestrantes, en el caso de la obtención de aceites minerales y en agentes para el tratamiento de metales, como aditivos para aceites minerales;como agentes protectores contra la corrosión en usos en agentes de lavado y limpieza;en usos electrónicos;como agentes captadores de radicales en capas fotosensibles;como agentes captadores de aldehídos;como agentes captadores de formaldehído en masas adhesivas, y cuerpos moldeados.
- 9Masa de moldeo polimérica termoplástica ignifugada, que contiene de 0,5 a 45 % en peso de un ácido etilendifosfínico de acuerdo con la reivindicación 1 o 2 y de 0,5 a 99,5 % en peso de un polímero termoplástico o de mezclas del mismo, siendo la suma de los componentes de 100 % en peso.
- 10Masa termoestable ignifugada, que contiene de 0,1 a 45 % en peso de un ácido etilendifosfínico de acuerdo con la reivindicación 1 o 2, de 40 a 89,9 % en peso de poliésteres insaturados y de 10 a 60 % en peso de un monómero vinílico, siendo la suma de los componentes de 100 % en peso.
- 11Resina epoxídica aprestada de manera ininflamable, que contiene de 0,5 a 50 % en peso de un ácido etilendifosfínico de acuerdo con por lo menos la reivindicación 1 o 2, de 5,5 a 99,5 % en peso de una resina epoxídica y de 0 a 20 % en peso de un agente endurecedor, siendo la suma de los componentes de 100 % en peso.
Independent claims11
363 paragraphs in 8 sections, as filed
Ethylenediphosphinic acids
The invention relates to ethylenediphosphinic acids, a process for their preparation and their use.
Ethylenediphosphinic acids are fundamentally known from the state of the art. Thus, the German patent application document DE-A-199 12 920 and the international patent application document WO-A-0 157 050 describe phosphonic acids of the HP (O) (OX) type - [CH2CH2-P ( O) (OX)] nH with X equal to H, a metal or an alkyl group and n greater than 1. These phosphonic acids are oligomeric or polymeric. They are prepared by procedures that produce telomeres, which, however, do not allow any access to phosphine acids with a specific chain length.
Therefore, a mission of the present invention is to make available ethylenediphosphinic acids, which in each case have a specific chain length and, therefore, can be "made to measure" for their respective purpose of use.
In the database DATABASE [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO; US; PODLAHOVA; JANA AND COLLABORATORS: "Compounds structurally related to complexons. XX. Hydrolysis of ethylenediphosphinetetraacetate anions" (Compounds structurally related to complexons. XX. Hydrolysis of ethylenediphosphine tetraacetate anions found in the STN Database (STN database) accession 1984: 51700 describes the preparation of an ethylenediphosphinic acid passing through ethylenediphosphine diacetate as an intermediate. Compounds of the formula (I) with A = CR5R6OH have not been described so far within the state of the art.
Accordingly, ethylenediphosphinic acids and their salts of the general formula constitute an object of the invention
(I)
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A (I)
in which A represents CR5R6-OH,
R1, R2, R3, R4, R5 and R6 are the same or different and mean, independently of each other, H, C1-C20 alkyl, C6-C20 aryl and / or C6-C20 aralkyl and
X represents H, an alkali metal, an element of the second main and secondary group, an element of the third main and secondary group, an element of the fourth main and secondary group, an element of the fifth main and secondary group, an element of the sixth secondary group , an element of the seventh secondary group, an element of the eighth secondary group and / or a nitrogen base.
Preferably, R1, R2, R3, R4, R5 and R6 are the same or different and mean, independently of each other, H, methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
The invention also relates to a process (1) for the preparation of ethylenediphosphinic acids and their salts of the general formula (I)
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A (I)
in which A is equal to CR5R6-OH,
R1, R2, R3, R4, R5 and R6 are the same or different and mean, independently of each other, H, C1-C20 alkyl, C6-C20 aryl and / or C6-C20 aralkyl and
X represents H or an alkali metal, characterized in that
a) an adduct of a monophosphinic acid of the formula (II) is reacted
HP (O) (OX) -A (II)
with acetylene or with an acetylene compound and
b) the ethylenediphosphinic acids of the type AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A are optionally separated with respect to the secondary products.
The invention also relates to a process (2) for the preparation of salts of ethylene bis (hydroxyalkylphosphinic acids) or salts of ethylenediphosphinic acids of type AP (O) (OX) -CR1R2-CR3R4-P (O) (OX ) -A, wherein A, R1, R2, R3, R4, R5 and R6 have the same meanings as in claim 1 and X means an alkali metal, an element of the second main and secondary group, an element of the third group main and secondary, an element of the fourth main and secondary group, an element of the fifth major and secondary group, an element of the sixth secondary group, an element of the seventh secondary group, an element of the eighth secondary group and / or a nitrogenous base, characterized in that an ethylene-bis- (hydroxyalkylphosphinic acid) or an acid ethylene diphosphine type AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, wherein A, R1, R2, R3, R4, R5 and R6 have the same meanings as in claim 1 and X means H, it is reacted within a solvent system with a participant I in the reaction, in which case it is a compound of an alkali metal, an element of the second main and secondary group, an element of the third main group and secondary, of an element of the fourth primary and secondary group, of an element of the fifth primary and secondary group, of an element of the sixth secondary group, of an element of the seventh secondary group, of an element of the eighth secondary group and / or a nitrogenous base.
The invention also relates to a process (3) for the preparation of salts of ethylene bis (hydroxyalkylphosphinic acids) or salts of ethylenediphosphinic acids of the type
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A
wherein A, R1, R2, R3, R4, R5 and R6 have the same meanings as in claim 1 and X means an element of the second main and secondary group, an element of the third main and secondary group, an element of the fourth primary and secondary group, an element of the fifth primary and secondary group, an element of the sixth secondary group, an element of the seventh secondary group, an element of the eighth secondary group and / or a nitrogen base, characterized in that an ethylene-bis- (hydroxyalkylphosphinic acid) or an ethylenediphosphinic acid type
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A
wherein A, R1, R2, R3, R4, R5 and R6 have the same meanings as in claim 1 and X means an alkali metal, it is reacted within a solvent system with a participant II in the reaction to give another salt of a metal (salt of a non-alkali metal).
Preferably, in the case of the participant II in the reaction, these are borates, carbonates, hydroxycarbonates, hydroxycarbonates, mixed hydroxocarbonates, mixed hydroxycarbonates, hydrates, phosphates, sulfates, sulfates, hydrates, hydroxosulfates hydrates, mixed hydroxosulfates hydrates, oxysulfates, acetates, nitrates, fluorides, fluorides hydrates, chlorides, chlorides hydrates, oxychlorides, bromides, iodides, iodides hydrates, derivatives of carboxylic acids and / or alkoxides.
The invention also relates to the use of ethylenediphosphinic acids according to at least one of claims 1 to 5 as flame retardants, in particular flame retardants for clear varnishes and intumescent coatings, fireproofing agents for wood and other cellulose-containing products, as reactive and / or non-reactive flame retardant agents for polymers, for the production of flame retardant polymeric molding masses, for the production of flame-retardant polymeric molded bodies and / or for the non-flammable sizing of polyesters and fabrics made purely of cellulose and mixed cellulose fabrics by impregnation.
The use of ethylenediphosphinic acids according to the invention and / or their salts as binding agents is preferred, eg for foundries and molding sands.
The use of ethylenediphosphinic acids according to the invention and / or their salts as crosslinking or accelerating agents is preferred in the case of the hardening of epoxy resins, polyurethanes and unsaturated polyester resins.
The use of ethylenediphosphinic acids according to the invention and / or their salts as polymer stabilizing agents is preferred, eg as a stabilizing agent for lightning protection, radical scavenging agents and / or tissue stabilizing agents of cotton, polymeric fibers and synthetic materials.
The use of ethylenediphosphinic acids according to the invention and / or their salts as phytoprotective agents is preferred, eg as a plant growth regulating agent, or as a herbicide, pesticide or fungicide.
The use of ethylenediphosphinic acids according to the invention and / or their salts as sequestering agents is preferred, eg for the control of depositions in industrial systems of water pipes, in the case of obtaining mineral oils and agents for the treatment of metals.
The use of ethylenediphosphinic acids according to the invention and / or their salts is preferred as an additive for mineral oils eg as an antioxidant agent, and to increase the octane number.
The use of ethylenediphosphinic acids according to the invention and / or their salts as corrosion protection agents is preferred.
The use of ethylenediphosphinic acids according to the invention and / or their salts in use in washing and cleaning agents is preferred, eg as a bleaching agent.
The use of ethylenediphosphinic acids according to the invention and / or their salts in electronic uses is preferred, e.g. in polyelectrolytes for capacitors, batteries and accumulators, as well as as radical scavenging agents in photosensitive layers.
The use of ethylenediphosphinic acids according to the invention and / or their salts as aldehyde picking agents is preferred. Surprisingly, it was found that ethylenediphosphinic acids according to the invention can be used to decrease the release of aldehydes. Preferred aldehydes are formaldehyde and acetaldehyde.
Aldehyde picking agents find a preferred use in adhesive masses, molded bodies eg in construction uses, in the automotive, nautical, aeronautical and aerospace industries and for electrical engineering, etc.
The invention also relates to a flame retardant thermoplastic polymeric molding mass, containing from 0.5 to 45% by weight of an ethylenediphosphinic acid according to claim 1 or 2 and from 0.5 to 99.5% by weight of a thermoplastic polymer or mixtures thereof, the sum of the components being 100% by weight.
The invention also relates to a flame retardant thermosetting mass, containing from 0.1 to 45% by weight of an ethylenediphosphinic acid according to claim 1 or 2, from 40 to 89.9% by weight of an unsaturated polyester and of 10 to 60% by weight of a vinyl monomer, the sum of the components being 100% by weight.
The invention also relates to an epoxy resin non-flammable, containing from 0.5 to 50% by weight of an ethylenediphosphinic acid according to claim 1 or 2, from 5 to 99.5% by weight of a resin epoxy and from 0 to 20% by weight of a hardening agent, the sum of the components being 100% by weight.
Preferably, A means H and X means Li, Na, K; Mg, Ca, Zn, Sr; Al, Ce, La; Ge, Sn, Pb, Ti, Zr; Sb, Bi; Cr, Mo, W; Mn; Faith, Co or Ni. Especially preferably, A means H and X means H, Na, Al, Zn, Ca, Mg, Ti or melamine. Preferred ethylenediphosphinic acids correspond to the formula
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to H and, when X is equal to H , result in an ethylenediphosphinic acid of the formula
HP (O) (OH) -CH2-CH2-P (O) (OH) -H; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula HP (O) (ONa) -CH2-CH2-P (O) (ONa) -H; and, when X is equal to aluminum, that is to say Al1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula HP (O) (O Al1 / 3) -CH2-CH2-P (O) (O Al1 / 3) -H; and, when X is equal to melamine, that is Mel, they result in a melamine salt of an ethylenediphosphinic acid of the formula HP (O) (OMel) -CH2-CH2-P (O) (OMel) -H. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 and R6 equal to H, and, when X is equal to H, result in an ethylenediphosphinic acid of the formula HO-CH2-P (O) (OH) -CH2-CH2-P (O) ( OH) -CH2-OH; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula HO-CH2-P (O) (ONa) -CH2-CH2-P (O) (ONa ) -CH2-OH; and, when X is equal to Al, that is to say Al1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula
HO-CH2-P (O) (O Al1 / 3) -CH2-CH2-P (O) (O Al1 / 3) -CH2-OH;
and, when X is equal to melamine, that is Mel, they result in a melamine salt of an ethylenediphosphinic acid of the formula HO-CH2-P (O) (OMel) -CH2-CH2-P (O) (OMel ) -CH2-OH. Preferred ethylenediphosphinic acids correspond to the formula
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 equal to CH3, and R6 equal to H, and, when X is equal to H, they result in an ethylenediphosphinic acid of the formula
HO-CH (CH3) -P (O) (OH) -CH2-CH2-P (O) (OH) -CH (CH3) -OH; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula
HO-CH (CH3) -P (O) (ONa) -CH2-CH2-P (O) (ONa) -CH (CH3) -OH; and, when X equals zinc, that is Zn1 / 2, they result in a salt of an ethylenediphosphinic acid of the formula HO-CH (CH3) -P (O) (OZn1 / 2) -CH2-CH2-P (O) (OZn1 / 2) -CH (CH3) -OH; and, when X is equal to ammonium, that is to say NH4, they result in an ammonium salt of an ethylenediphosphinic acid
of the formula HO-CH (CH3) -P (O) (ONH4) -CH2-CH2-P (O) (ONH4) -CH (CH3) -OH. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 equal to phenyl, and R6 equal to H, and, when X is equal to H, result in an ethylenediphosphinic acid of the formula HO-CH (phenyl) -P (O) (OH) -CH2- CH2-P (O) (OH) -CH (phenyl) -OH; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula
HO-CH (phenyl) -P (O) (ONa) -CH2-CH2-P (O) (ONa) -CH (phenyl) -OH; and, when X is equal to titanium, that is Ti1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula HO-CH (phenyl) -P (O) (OTi1 / 3) -CH2-CH2-P (O) (OTi1 / 3) -CH (phenyl) -OH; and, when X equals melamine, that is Mel, they result in a melamine salt of an acid
ethylenediphosphin of the formula HO-CH (phenyl) -P (O) (OMel) -CH2-CH2-P (O) (OMel) -CH (phenyl) -OH. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 and R6 equal to CH3, and, when X equals H, results in an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OH) -CH2-CH2-P (O) (OH) -C (CH3) 2-OH; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (ONa) -CH2-CH2-P ( O) (ONa) -C (CH3) 2-OH; and, when X is equal to magnesium, that is to say Mg1 / 2, they result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OMg1 / 2) -CH2-CH2- P (O) (OMg1 / 2) -C (CH3) 2-OH;
and, when X is equal to melamine, that is Mel, they result in a melamine salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OMel) -CH2-CH2-P ( O) (OMel) -C (CH3) 2-OH. Preferred ethylenediphosphinic acids also correspond to the formula
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 equal to CH3, and R6 equal to C2H5, and, when X is equal to H, they result in an ethylenediphosphinic acid of the formula
HO-C (CH3) (C2H5) -P (O) (OH) -CH2-CH2-P (O) (OH) -C (CH3) (C2H5) -OH; and, when X is equal to an alkali metal, preferably K results in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) (C2H5) -P (O) (OK) -CH2-CH2-P (O) (OK) -C (CH3) (C2H5) -OH; and, when X is equal to aluminum, that is to say Al1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) (C2H5) -P (O) (OAl1 / 3) -CH2- CH2-P (O) (OAl1 / 3) -C (CH3) (C2H5) -OH; and, when X is equal to ammonium, that is NH4, they result in an ammonium salt of an ethylenediphosphinic acid of the formula HO-C (CH3) (C2H5) -P (O) (ONH4) -CH2-CH2- P (O) (ONH4) -C (CH3) (C2H5) -OH. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 equal to CH3, and R6 equal to phenyl, and, when X is equal to H, result in an ethylenediphosphinic acid of the formula HO-C (CH3) (phenyl) -P (O) (OH) -CH2-CH2-P (O) (OH) -C (CH3) (phenyl) -OH; and, when X is equal to an alkali metal, preferably Li, they result in a salt of an ethylenediphosphinic acid of the formula
HO-C (CH3) (phenyl) -P (O) (OLi) -CH2-CH2-P (O) (OLi) -C (CH3) (phenyl) -OH; and, when X is equal to zinc, that is Zn1 / 2, they result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) (phenyl) -P (O) (OZn1 / 2) -CH2- CH2-P (O) (OZn1 / 2) -C (CH3) (phenyl) -OH; and, when X equals melamine, that is Mel, they result in a melamine salt of an acid
ethylenediphosphin of the formula HO-C (CH3) (phenyl) -P (O) (OMel) -CH2-CH2-P (O) (OMel) -C (CH3) (phenyl) -OH. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1 is equal to methyl, R2, R3 and R4 are equal to H and A is equal to H, and, when X is equal to H, they result in an ethylenediphosphinic acid of the formula HP (O) (OH) -CH (CH3) -CH2-P (O) (OH) -H; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula HP (O) (ONa) -CH (CH3) -CH2-P (O) (ONa) -H; and, when X is equal to Al, that is to say Al1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula
HP (O) (OAl1 / 3) -CH (CH3) -CH2-P (O) (OAl1 / 3) -H;
and, when X equals melamine, that is Mel, they result in a melamine salt of an ethylenediphosphinic acid of the formula HP (O) (OMel) -CH (CH3) -CH2-P (O) (OMel) -H ;. Preferred ethylenediphosphinic acids also correspond to the formula
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1 is equal to methyl, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 and R6 equal to CH3, and, when X is equal to H, result in an ethylenediphosphinic acid of the formula
HO-C (CH3) 2-P (O) (OH) -CH (CH3) -CH2-P (O) (OH) -C (CH3) 2-OH; and, when X is equal to an alkali metal, preferably K, result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OK) -CH (CH3) -CH2 -P (O) (OK) -C (CH3) 2-OH; and, when X is equal to magnesium, that is to say Mg1 / 2, they result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OMg1 / 2) -CH (CH3) -CH2-P (O) (OMg1 / 2) -C (CH3) 2-OH; and, when X equals ammonium, that is NH4, they result in an ammonium salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (ONH4) -CH (CH3) -CH2 -P (O) (ONH4) -C (CH3) 2-H. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1 is equal to phenyl, R2, R3 and R4 are equal to H and A is equal to H, and, when X is equal to H, they result in an ethylenediphosphinic acid of the formula HP (O) (OH) -CH (phenyl) -CH2-P (O) (OH) -H; and, when X is equal to an alkali metal, preferably Na, they result in a salt of an ethylenediphosphinic acid of the formula HP (O) (ONa) -CH (phenyl) -CH2-P (O) (ONa) -H; and, when X is equal to Al, that is to say Al1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula HP (O) (OAl1 / 3) -CH (phenyl) -CH2-P (O) ( OAl 1/3) -H; and, when X equals melamine, that is Mel, they result in a melamine salt of an ethylenediphosphinic acid of the formula HP (O) (OMel) -CH (phenyl) -CH2-P (O) (OMel) -H. Preferred ethylenediphosphinic acids also correspond to the formula AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A, in which R1 is equal to phenyl, R2, R3 and R4 are equal to H and A is equal to CR5R6-OH with R5 and R6 equal to CH3, and, when X is equal to H, they result in an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OH) -CH (phenyl) -CH2-P (O) (OH) -C (CH3) 2-OH; and, when X is equal to an alkali metal, preferably K, they result in a salt of an ethylenediphosphinic acid of the formula HO-C (CH3) 2-P (O) (OK) -CH (phenyl) -CH2 -P (O) (OK) -C (CH3) 2-OH; and, when X is equal to titanium, that is Ti1 / 3, they result in a salt of an ethylenediphosphinic acid of the formula
HO-C (CH3) 2-P (O) (OTi1 / 3) -CH (phenyl) -CH2-P (O) (OTi1 / 3) -C (CH3) 2-OH;
and, when X is equal to ammonium, that is NH4, they result in an ammonium salt of an ethylenediphosphinic acid of the formula
HO-C (CH3) 2-P (O) (ONH4) -CH (phenyl) -CH2-P (O) (ONH4) -C (CH3) 2-H. Preferred nitrogenous bases are ammonium, substituted ammonium, ethylenediamine, hydroxylamine, urea, alicyclic compounds with N such as pyrrolidine, piperidine, imidazolidine, piperazine, aromatic compounds with N such as heteroaromatic ring compounds such as pyrrole, pyridine, imidazole, pyrazine, substituted urea derivatives (e.g. dimethyl urea, N, N'-diphenyl urea, benzyl urea, acetylene urea, tetramethyl urea), thiourea, acetylene urea, guanidine, substituted guanidine derivatives, (eg an alkyl-guanidine, a aryl guanidine, diphenyl guanidine), biguanide, melamine, substituted melamine derivatives, (eg ethylene dimelamine), condensation products of melamine and compounds with a higher degree of condensation thereof, such as e.g. . melem, melam or melon, melamine and phenol systems, benzoguanamine, acetoguanamine, urethanes, cyanamide, dicyandiamide, aniline, sulfonamide, biuret, allantoin, tolyltriazole, benzotriazole, 2-amino-4-methyl-pyrimidine, hydantoin substituted derivatives (eg 5,5-diphenyl-hydantoin), ammonium amide of malonic acid, ethylene-bis-5-triazone, glycine anhydride and arbitrary mixtures thereof.
Preferred alkali metals are sodium and potassium.
Preferably, the reaction of the adduct of a monophosphinic acid takes place according to the procedure (1) with acetylene a) in the presence of a solvent and a radical initiating agent, b) previously having an adduct of a monophosphinic acid and a solvent , and adding
Dosing acetylene and the initiating agent separately (optionally within a solvent), c) previously disposing an adduct of a monophosphinic acid, acetylene and a solvent, and dosing the initiating agent (optionally within a solvent) ), d) by previously disposing an adduct of a monophosphinic acid, a solvent and an initiating agent, and dosing acetylene (optionally within a solvent), e) by previously disposing an adduct of a monophosphinic acid, acetylene, a solvent and an initiating agent. The separation of the product according to the procedure (1) is preferred by a) a separation of the solid-liquid type (e.g. by filtration, centrifugation, sedimentation) b) a separation of the liquid-liquid type (e.g. by extraction, etc.).
Preferred adducts according to the procedure (1) are those obtained with aldehydes and / or ketones. Preferred aldehydes according to the procedure (1) are aliphatic aldehydes (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, acrolein, crotonaldehyde, propargyl aldehyde) and / or aromatic aldehydes (benzaldehyde, p-tolylaldehyde, anisaldehyde or salicylaldehyde, vanillin).
Preferred ketones according to the procedure (1) are aliphatic ketones (acetone, methyl ethyl ketone, chloroacetone, methyl vinyl ketone, mesityl oxide, forone or aromatic ketones (acetophenone, benzophenone). Preferred aldehydes are aliphatic aldehyde carboxylic acids (eg glyoxylic acid). Preferred ketones are aliphatic ketocarboxylic acids (pyruvic acid, acetoacetic acid, levulinic acid). Preferred aldehydes are aliphatic hydroxyaldehydes (glycollaldehyde, glycerlaldehyde). Preferred aldehydes are aliphatic hydroxyketones (acetol, acetoin, dihydroxyacetone). Preferred aldehydes are aliphatic dialdehydes (glyoxal, malonodialdehyde, succinodialdehyde). Preferred aldehydes are ketoaldehydes (methylglyoxal).
Preferred ketones are diketones (diacetyl, acetylacetone, acetonylacetone). Fundamentally, as radical initiating agents according to the procedure (1) all the systems, which generate free radicals. The reaction by adding the olefin can be initiated by an agent anionic initiator, an initiator agent by radicals or by photochemical means.
Especially preferred radical initiating agents are peroxy compounds such as peroxomonosulfuric acid, potassium persulfate (potassium peroxomonosulfate), Caroat (®), Oxone (®), peroxodisulfuric acid, potassium persulfate (potassium peroxodisulfate), sodium persulfate (sodium peroxodisulfate) and ammonium persulfate (ammonium peroxodisulfate).
Especially preferred are compounds, which in the solvent system may form peroxides, such as sodium peroxide, sodium peroxide diperoxohydrate, sodium peroxide diperoxohydrate hydrate, sodium peroxide dihydrate, sodium peroxide octahydrate, lithium peroxide, lithium peroxide monoperoxohydrate trihydrate, calcium peroxide, strontium peroxide, barium peroxide, magnesium peroxide, zinc peroxide, potassium hyperoxide, potassium peroxide diperoxohydrate, sodium peroxoborate tetrahydrate, sodium peroxoborate trihydrate, sodium peroxoborate monohydrate, anhydrous sodium peroboborate, potassium peroxoborate peroxohydrate, magnesium peroxoborate, calcium peroxoborate, barium peroxoborate, strontium peroxoborate, potassium peroxophosphoric acid, peroxophosphoric acid, peroxophosphoric acid , potassium peroxodiphosphate, ammonium peroxodiphosphate, potassium and ammonium peroxodiphosphate (double salt), sodium carbonate peroxohydrate, urea peroxohydrate, ammonium oxalate peroxide, barium peroxide perohydrate, hydrogen and calcium peroxides, calcium peroxide peroxohydrate, diperoxophosphate of ammonium triphosphate hydrate, potassium fluoride peroxohydrate, potassium fluoride triperoxohydrate, potassium fluorophosphate dihydrogen phosphate diperoxohydrate, sodium pyrophosphate diperoxohydrate octahydrate, potassium acetate peroxohydrate, sodium phosphate peroxohydrate and sodium silicate peroxohydrate.
Especially preferred are hydrogen peroxide, perforic acid, peracetic acid, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichloro-benzoyl peroxide, decanoyl peroxide, lauryl peroxide, cumene hydroperoxide , pinene hydroperoxide, p-methane hydroperoxide, t-butyl hydroperoxide, acetyl-acetone peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxyaleic acid, t-butyl peroxybenzoate and acetyl-cyclohexylsulfonyl peroxide.
Preferably, water soluble azo compounds are used as radical initiating agents.
In addition, azoic initiating agents such as 2-t-butylazo-2-cyanopropane, dimethyl azo diisobutyrate, azodiisobutyronitrile, 2-t-butylazo-1-cyano-cyclohexane, 1-t-amylazo-1-cyano- are preferred. cyclohexane In addition, alkyl-barnatals such as 2,2-bis- (t-butyl-peroxy) butane, ethyl-3,3-bis (t-butyl-peroxy) butyrate, 1,1-di- (t-butylperoxy) are preferred ) -cyclohexane.
Especially preferred are azoic initiating agents such as ®VAZO 52, ®VAZO 64 (AIBN), ®VAZO 67, ®VAZO 88, ®VAZO 44, ®VAZO 56, ®VAZO 68 of the Dupont-Biesteritz entity, V-70 2 , 2'-azobis (4-methoxy-2,4-dimethyl-valeronitrile), V-65 2,2'-azobis (2,4-dimethyl-valeronitrile), V-601 2,2'-azobis (2'-methyl dimethylpropionate), V59 2,2'-azobis (2-methyl-butyronitrile), V-40, VF-096 1,1'-azobis (cyclohexane-1-carbonitrile), V-30 1 - [(cyano -1-methylethyl) azo] formamide, VAm-110 2,2'-azobis (N-butyl-2-methyl-propionamide), Am-111 2,2'-azobis (N-cyclohexyl-2-methylpropionamide], VA-041 2,2'- dihydrochloride azobis [2- (5-methyl-2-imidazolin-2-yl) propane], VA-044 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride], VA-046B disulfate of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrates, V50 2,2'-azobis (2-amidino-propane) hydrochloride, VA-057 2,2'-azobis [ N- (2-carboxy-ethyl) -2-methyl-propionamidine] tetrahydrate, VA-058 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, VA-060 2,2'-azobis dihydrochloride {2- [1- ( 2-hydroxy-ethyl) -2-imidazolin-2-yl] propane}, VA-061 2,2'-azobis [2- (2-imidazolin-2-yl) propane], VA080 2,2'-azobis { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy-ethyl] propionamide, VA-085 2,2'-azobis [2-methyl-N- [2- (1-hydroxybutyl)] propionamide ] and VA-086 2,2'-azobis [2-methyl-N- (2-hydroxy-ethyl) propionamide] from Wako Chemicals.
For the preparation according to the procedure (1) a solvent can be used. Solvents according to the invention are preferably water, alcohols, such as, for example, methanol, ethanol, iso-propanol, n-propanol, nbutanol, iso-butanol, t-butanol, n-amyl alcohol, iso-amyl alcohol , t-amyl alcohol, n-hexanol, n-octanol, isooctanol, n-tridecanol, benzyl alcohol, etc. Glycols such as e.g. are also preferred. ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, di (ethylene glycol), etc .; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and petroleum ether, petroleum benzine, kerosene, petroleum, paraffin oil etc .; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethyl benzene, diethyl benzene, etc .: halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, tetrachlorocarbon, tetrabromoethylene, etc .; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane etc .: ethers such as anisole (methyl-phenyl ether), t-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether, etc .; glycol ethers such as di (ethylene glycol) -diethyl ether, di (ethylene glycol) -dimethyl ether (diglyme), di (ethylene glycol) -monobutyl ether, di (ethylene glycol) -monomethyl ether, 1,2-dimethoxy- ethane (DME monoglyme), ethylene glycol monobutyl ether, tri (ethylene glycol) -dimethyl ether (triglyme), tri (ethylene glycol) -monomethyl ether etc .; ketones such as acetone, diisobutyl ketone, methyl-n-propyl ketone; methyl ethyl ketone, methyl isobutyl ketone, etc .; esters such as methyl formate, methyl acetate, ethyl acetate, n-propyl acetate and n-butyl acetate, etc .; carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, etc. One or more of these compounds can be used alone or in combination.
According to the process (1), a ratio between the solvent and the adduct of a monophosphinic acid of 100 by 1 to 1 per 100 is preferred according to the invention, especially preferably from 10 by 1 to 1 per 10 parts by weight.
According to the process (1), a ratio between the initiating agent and the adduct of a monophosphinic acid of 1 by 1 to 1 per 1,000 is preferred according to the invention, especially preferably 1 to 2 to 1 per 100 mol / mol.
According to the process (1), a ratio between acetylene and the adduct of a monophosphinic acid of 100 by 1 to 1 per 100 is preferred according to the invention, especially preferably from 5 by 1 to 1 per 5 mol / mol.
According to the method (1), a reaction time period of 0.1 to 100 h is preferred according to the invention, especially preferably 1 to 10 h.
According to the invention it is preferred to purify the phosphonic acid of the type
HO-CR5R6-P (O) (OX) -CR1R2-CR3R4-P (O) (OX) -CR5R6OH.
A preferred purification procedure according to procedure (1) consists of
a) a recrystallization from the solvent according to the invention and a separation
b) a digestion with a solvent according to the invention and a separation.
A preferred relationship between the solvent and the phosphinic acid of the type
HO-CR5R6-P (O) (OX) -CR1R2-CR3R4-P (O) (OX) -CR5R6OH for the preferred purification procedure according to procedure (1) is 1,000 by 1 to 4 by 1, especially Preferred from 100 by 1 to 1 by 1.
A preferred temperature for the purification process according to procedure (1) is 20 to 200 ° C, especially preferably 50 to 150 ° C.
A preferred pressure for the purification process according to procedure (1) is 10 to 100,000,000 Pa.
According to the procedure (1) a purity of greater than 90% is preferred, especially preferably greater than 95%.
The invention also relates to a process for the preparation of the salts of ethylene bis (hydroxyalkylphosphinic acids) and the salts of ethylenediphosphinic acids, in which the acids are transformed into aluminum salts or respectively the alkali metal salts are transformed. in aluminum salts.
According to the invention, a process (2) is preferred in which an ethylene-bis- (hydroxyalkylphosphinic acid) or an ethylenediphosphinic acid according to the invention, with X equal to H, is reacted within a suitable solvent system with a participant A in the reaction.
Preferably, in a process (3), the salt according to the invention of ethylene-bis- (hydroxyalkylphosphinic acid) or ethylenediphosphinic acid according to the invention, with X equal to an alkali metal, can be transformed into a solvent suitable by adding another component B, in another metal salt.
Preferably, the reaction of the phosphinic acid according to the invention with component A is carried out according to procedure (2) in the case of a solid material content of the salts of the phosphonic acids according to the invention from 0.1 to 70% by weight, preferably 5 to 40% by weight.
The reaction according to process (2) is preferably carried out at a temperature of -20 to +500 ° C, especially preferably 70 to 160 ° C.
Preferably, the ratio between component A and phosphorus (of the phosphinic acid according to the invention) according to the process (2) is 0.8 to 3 equivalent of ions (moles per cation electric charge), especially preferably from 1 to 2.
Preferably, the ratio between the solvent and the phosphorus (of the phosphinic acid according to the invention) according to the process (2) is from 2 to 1,000 mol / mol, especially preferably from 4 to 100 mol / mol.
A preferred solvent system according to the invention according to the process (2) has a dissociation constant pKa of 10 to 30.
A preferred component A according to the invention according to the process (2) is a salt of an element of the first main group, preferably an alkali metal hydroxide, an alkali metal hydroxide oxide, an alkali metal hydroxide carbonate, a Alkali metal alcoholate, especially preferably lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium n-propylate, sodium i-propylate, sodium n-butylate, sodium i-butylate, tert-sodium butylate, sodium amylate and sodium glycolate.
A preferred component A according to the invention according to the process (2) is a salt of an element of the first main group, preferably an element of the second main and secondary group, preferably an alkaline earth metal hydroxide, an oxide- alkaline earth metal hydroxide, an alkaline earth metal hydroxide carbonate, especially preferably magnesium hydroxide (® Magnifin H5, from Albermarle), hydrotalcites (Mg6Al2 (OH) 16CO3 * nH2O), dihydrotalcite, magnesium carbonates or magnesium and calcium carbonates, calcium hydroxide, basic zinc carbonate, zinc hydroxide carbonate, zinc carbonate basic hydrate, zinc hydroxides or mixed zinc oxide-hydroxides (a classic zinc oxide, p. Cricket, an activated zinc oxide, eg Rheinchemie, zincite, calamine), and a zinc hydroxystanate.
A preferred component A according to the invention according to the process (2) is a salt of an element of the third main and secondary group, preferably aluminum hydroxide, cerium hydroxide, lanthanum hydroxide, an aluminum alcoholate, a cerium alcoholate , a lanthanum alcoholate, aluminum hydroxide or a mixed aluminum oxide-hydroxide, sodium dihydroxyaluminium carbonate, NaAl (OH) 2CO3 and / or poly (aluminum-hydroxy) compounds, which preferably have an aluminum content of 9 to 40% by weight.
A preferred component A according to the invention according to the process (2) is a salt of an element of the fourth main and secondary group, preferably tin hydroxides, lead hydroxides, titanium oxide hydroxides, zirconium oxide hydroxides, alcoholates tin, titanium alcoholates and zirconium alcoholates.
Preferred titanium alcoholates according to the invention, ie titanium alkoxides, are titanium n-proproxide.
(IV) (®Tilcom NPT, ® Vertec NPT), titanium n-butoxide- (IV), titanium chloride triisopropoxide, titanium ethoxide- (IV), (2-ethyl-hexyl)-titanium oxide- ( IV) (®Tilcom EHT, ®Vertetec EHT).
One of the preferred tin alcoholates (tin alkoxides) according to the invention is tin tert-butoxide (IV).
One of the preferred zirconium alcoholates according to the invention, that is zirconium alkoxides, is zirconium tert-butoxide- (IV).
Preferred B components according to the invention according to the method (3) are borates, carbonates, hydroxycarbonates, hydroxycarbonates hydrates, mixed hydroxocarbonates, mixed hydroxycarbonates hydrates, phosphates, sulfates, sulfates hydrates, hydroxosulfates hydrates, mixed hydroxosulfates hydrates, oxysulfates, acetates, nitrates, fluorides, fluorides hydrates, chlorides, chlorides hydrates, oxychlorides, bromides, iodides, iodides hydrates, derivatives of carboxylic acids and / or alkoxides of elements of the first main group, the second main and secondary group - preferably Mg, Ca, Zn - or the third main and secondary group - preferably Al, Ce, La -.
Preferred B components according to the invention according to the process (3) are aluminum chloride, aluminum nitrate, aluminum sulfate, titanyl sulfate, zinc nitrate, zinc sulfate and / or zinc chloride.
Preferably, the reaction according to the procedure (3) is carried out in a vessel with stirring system, a mixer and / or a kneader.
Preferably, the reaction is carried out according to procedure (3) with an energy input of 0.083 to 1.65 kW / m3, particularly preferably 0.33 -1.65 kW / m3.
Preferably, the phosphonic acid salts according to the invention according to the process (3) are separated from the reaction mixture by filtration and / or centrifugation.
Preferably, the phosphonic acid salts according to the invention according to the method (3) are separated with pressure suction filters, vacuum suction filters, suction filters with stirring mechanism, spark plug filters, flat vane filters axial, circular flat vane filters, centrifugal disc filters, chamber / rack filtration presses, automatic chamber filtration presses, cell and vacuum drum filters, vacuum cell and disc filters, internal vacuum cell filters, flat vacuum cell filters, rotary pressure filters or vacuum band filters.
Preferably, the filtration pressure according to the procedure (3) is 0.5 Pa at 6 MPa.
Preferably, the filtration temperature according to the procedure (3) is from 0 to 400 ° C.
Preferably, the specific filtration efficiency according to the procedure (3) is from 10 to 200 kg * h-1 * m-2.
Preferably, the residual moisture of the filter cake according to the procedure (3) is 5 to 60%.
Preferably, the salts of ethylene-bis- (hydroxyalkylphosphinic acids) or ethylenediphosphinic acids according to the invention according to the method (3) are separated with full-wrap centrifuges, such as overflow centrifuges, detachment centrifuges, chamber centrifuges, worm discharge centrifuges, plate centrifuges, tube centrifuges, sieve centrifuges such as pendulum and hanging centrifuges, worm and sieve screw centrifuges, detachment centrifuges and with push sieves or centrifuges.
Preferably, the acceleration ratio according to the procedure (3) is from 300 to 15,000.
Preferably, the throughput flow of suspensions according to the procedure (3) is from 2 to 400 m3 * h-1.
Preferably, the throughput of solid materials through the process (3) is from 5 to 80 t * h-1.
Preferably, the residual moisture of the cake according to the procedure (3) is 5 to 60%.
Preferably, according to the method (3), the salts of the phosphine acids according to the invention are dried.
Equipment according to the invention for drying according to the procedure (3) are chamber dryers, channel dryers, band dryers (air velocity 2 -3 m / s), dish dryers (temperature from 20 to 400 ° C), drum dryers (hot gas temperature 100 - 250 ºC), vane vane dryers (temperature 50 - 300 ºC), circulating current dryers (air speed 10 - 60 m / s, outlet air temperature 50 - 300 ºC ), fluidized bed dryers (air velocity 0.2 - 0.5 m / s, outlet air temperature 50 - 300 ºC), cylinder dryers, tubular dryers (temperature from 20 to 200 ºC), vane vane dryers, vacuum drying ovens (temperature from 20 to 300 ° C, pressure 0.001 - 0.016 MPa), vacuum cylinder dryers (temperature from 20 to 300 ° C, pressure 0.004 - 0.014 MPa), vacuum blade vane dryers (temperature of 20 at 300 ° C, pressure 0.003 - 0.02 MPa), Conical vacuum dryers (temperature from 20 to 300 ° C, pressure 0.003 - 0.02 MPa).
According to the invention, a process (4) for the formation of an ethylenediphosphinic acid according to the invention of type HP (O) (OH) -CR1CR2-CR3R4-P (O) (OH) -H from an ethylene-bis acid - (hydroxyalkylphosphine) according to the invention of the HO-CR5R6-P (O) (OX) -CR1R2-CR3R4-P (O) (OX) -CR5R6OH type.
An embodiment according to the invention of the process (4) consists in heating the ethylene-bis (hydroxyalkylphosphinic acid) according to the invention of the type HO-CR5R6-P (O) (OX) -CR1R2-CR3R4-P (O) (OX ) -CR5R6-OH.
A preferred temperature for the formation process according to the process (4) is from 20 to 300 ° C, especially preferably from 50 to 200 ° C.
A preferred pressure for the formation process according to the procedure (4) is from 10 to 100,000,000 Pa.
According to the procedure (4) a relationship between protonic acid and ethylene-bis (hydroxyalkylphosphinic acid) according to the invention of the HO-CR5R6-P (O) (OX) -CR1R2-CR3R4-P (O) (OX) type is preferred ) -CR5R6-OH from 100 by 1 to 1 by 100, especially preferably from 10 by 1 to 1 per 10 mol / mol.
Preferably, according to the procedure (4) the protonic acid is removed. The elimination is preferably carried out by distillation separation, extraction and / or crystallization separation.
A preferred temperature for the separation of the protonic acid according to the process (4) is from 20 to 300 ° C, especially preferably from 50 to 200 ° C.
A preferred pressure for the separation of the protonic acid according to the procedure (4) is from 10 to 108 Pa.
It is preferred according to the invention, according to the method (4), to carry out the heating in the presence of a solvent.
A preferred temperature for solvent removal according to process (4) is 20 to 300 ° C, especially preferably 50 to 200 ° C.
A preferred pressure for solvent removal according to procedure (4) is 10 to 108 Pa.
Preferably, ethylene-bis- (hydroxyalkylphosphinic acid) is used for the preparation of ethylenediphosphinic acid by separating the end groups (this is possible as alkali metal acids / salts / aluminum salts, etc.).
In this case, the use of phosphinic acid according to the invention and / or its salts of the type
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A
and of its derivatives with R1, R2, R3 and R4 equal to H, C1-C20 alkyl, aryl (preferably phenyl), and / or aralkyl, A equal to CR1R2OH, X equal to H, an alkali metal, Al , Zn, Ca, Mg, Ti, a nitrogen base (preferably NH4, ethylenediamine, melamine, etc.) for the preparation of phosphinic acid according to the invention and / or its salts of the type
AP (O) (OX) -CR1R2-CR3R4-P (O) (OX) -A
and of its derivatives with R1, R2, R3 and R4 equal to H, C1-C20 alkyl, aryl (preferably phenyl), and / or aralkyl,
Like H, X equals H, an alkali metal, Al, Zn, Ca, Mg, Ti, a nitrogen base (preferably NH4, ethylenediamine, melamine, etc.).
The use of phosphonic acid according to the invention and / or its salts is preferred for the production of flame-retardant polymeric molding masses.
Preferably, the flame retardant polymeric molding mass contains 0.5 to 45% by weight of the phosphinic acid according to the invention and / or its salts, 0.5 to 95% by weight of a polymer or mixtures thereof. , from 0.5 to 55% by weight of additives, from 0.5 to 55% by weight of a filler material or respectively of reinforcing materials, the sum of the components being 100% by weight.
Preferably, the flame retardant polymeric molding mass contains from 10 to 40% by weight of the phosphinic acid according to the invention and / or its salts, from 10 to 80% by weight of a polymer or mixtures thereof, from 2 to 40% by weight of additives, from 2 to 40% by weight of a filler material or respectively of reinforcing materials, the sum of the components being 100% by weight.
A process for the production of flame retardant polymeric molding masses is characterized in that the phosphonic acid according to the invention and / or its salt is mixed with the polymeric granulate and possibly with additives, and is incorporated in a two-screw extruder (ZSK 25 WLE, 14.5 kg / h, 200 rpm, L / D: 4) at temperatures of 170 ° C (for a polystyrene), about 270 ° C (for a PET, polyethylene terephthalate), 230 to 260 ° C (for a poly (butylene terephthalate), PBT), of 260 ° C (for a PA6), or respectively 260 to 280 ° C (for a PA 66). The homogenized polymer cord is removed, cooled in the water bath, then granulated and dried to a residual moisture content of 0.05 to 5%, preferably 0.1 to 1% by weight .
A process for the production of a flame retardant polymer molding mass is characterized in that 1,000 parts by weight of dimethyl terephthalate and 720 parts by weight of ethylene glycol and 35 to 700 parts by weight of a phosphonic acid according to the invention are polymerized. The polymerization can optionally be carried out in the presence of zinc acetate. Optionally, the flame retardant polymeric molding mass can be spun to form fibers.
Preferably, in the case of the polymer it is a thermoplastic or thermosetting polymer.
Preferably, in the case of thermoplastic polymers, these are mono-and diolefin polymers, for example, a polypropylene, a polyisobutylene, a poly (butene-1), a poly (4-methyl-pentene-1) ), a polyisoprene or a polybutadiene, as well as cycloolefin polymers such as eg cyclopentene or norbornene; also a polyethylene (which may eventually be crosslinked), e.g. a high density polyethylene (HDPE), a high density and high molecular mass polyethylene (HDPE-HMW), a high density and ultra high molecular mass polyethylene (HDPE-UHMW), a medium density polyethylene (MDPE) , a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched low density polyethylene (VLDPE), as well as mixtures thereof.
Preferably, in the case of thermoplastic polymers, they are copolymers of mono-and diolefins with each other or with other vinyl monomers, such as eg. copolymers of ethylene and propylene, a linear low density polyethylene (LLDPE) and mixtures thereof with a low density polyethylene (LDPE), copolymers of propylene and butene-1, copolymers of propylene and isobutylene, copolymers of ethylene and butene-1 , ethylene and hexene copolymers, ethylene and methylpentene copolymers, ethylene and heptene copolymers, ethylene and octene copolymers, propylene and butadiene copolymers, isobutylene and isoprene copolymers, copolymers of ethylene and an alkyl acrylate, copolymers of ethylene and an alkyl methacrylate, copolymers of ethylene and vinyl acetate and their copolymers with carbon monoxide, or copolymers of ethylene and acrylic acid and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; in addition mixtures of such copolymers with each other, eg. mixtures of a polypropylene and copolymers of ethylene and propylene, mixtures of LDPE's and copolymers of ethylene and vinyl acetate, mixtures of LDPE's and copolymers of ethylene and acrylic acid, mixtures of LLDPE's and copolymers of ethylene and vinyl acetate, mixtures of LLDPE's and copolymers of ethylene and acrylic acid, and mixtures of polyalkylenes and copolymers of carbon monoxide constituted alternately or statistically, and mixtures thereof with other polymers such as e.g. polyamides
Preferably, in the case of polymers, these are hydrocarbon resins (eg C5-C9), including hydrogenated modifications thereof (eg resins that confer tackiness) and mixtures of polyalkylenes and starches.
Preferably, in the case of thermoplastic polymers it is a polystyrene, a poly (p-methyl-styrene) and / or a poly (alpha-methyl-styrene).
Preferably, in the case of thermoplastic polymers, these are copolymers of styrene or alpha-methyl styrene with dienes or acrylic derivatives, such as e.g. those of styrene and butadiene, those of styrene and acrylonitrile, those of styrene and alkyl methacrylates, those of styrene, butadiene and acrylates and methacrylates of alkyl, those of styrene and maleic acid anhydride, those of styrene, acrylonitrile and methyl acrylate ; mixtures of styrene copolymers with high impact toughness (shock resistance) based on copolymers of styrene and another polymer, such as e.g. of a polyacrylate, a diene polymer or a terpolymer of ethylene, propylene and a diene; as well as block copolymers of styrene, such as those of styrene-butadiene styrene, those of styrene -isoprene-styrene, those of styrene -ethylene / butylene-styrene or those of styrene ethylene / propylene-styrene.
Preferably, in the case of thermoplastic polymers, these are styrene graft copolymers
or alpha-methyl styrene, such as e.g. those of styrene on a polybutadiene, those of styrene on copolymers of polybutadiene and styrene or copolymers of polybutadiene and acrylonitrile, those of styrene and acrylonitrile (or respectively methacrylonitrile) on a polybutadiene; those of styrene, acrylonitrile and methyl methacrylate on a polybutadiene; those of styrene and maleic acid anhydride on a polybutadiene; those of styrene, acrylonitrile and maleic acid anhydride or maleic acid imide on a polybutadiene; those of styrene and imide of maleic acid on a polybutadiene, those of styrene and alkyl acrylates or respectively alkyl methacrylates on a polybutadiene, those of styrene and acrylonitrile on terpolymers of ethylene, propylene and a diene, those of styrene and acrylonitrile on poly (alkyl acrylates) or poly (alkyl methacrylates), those of styrene and acrylonitrile on acrylate and butadiene copolymers, as well as mixtures thereof, such as those known eg. such as the polymers of ABS, MBS, ASA or AES.
Preferably, in the case of polymers, they are halogenated polymers, such as, for example, a polychloroprene, a chlorinated rubber, a chlorinated and brominated copolymer based on isobutylene and isoprene (a halobutyl rubber), a chlorinated polyethylene or chlorosulfonated, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of epichlorohydrin, in particular polymers based on halogenated vinyl compounds, such as e.g. a polyvinyl chloride, a polyvinylidene chloride, a polyvinyl fluoride, a polyvinylidene fluoride; as well as its copolymers, such as those of vinyl chloride and vinylidene chloride, those of vinyl chloride and vinyl acetate or those of vinylidene chloride and vinyl acetate.
Preferably, in the case of thermoplastic polymers, these are polymers, which are derived from unsaturated acids in alpha, beta and their derivatives, such as polyacrylates and polymethacrylates, poly (methyl methacrylates), poly (acrylamides) and poly (acrylonitriles) that have been modified with butyl acrylate to be shock resistant, and copolymers of said monomers with each other or with other unsaturated monomers, such as e.g. copolymers of acrylonitrile and butadiene, copolymers of acrylonitrile and alkyl acrylates, copolymers of acrylonitrile and alkoxyalkyl acrylates, copolymers of acrylonitrile and vinyl halides or acrylonitrile terpolymers, alkyl methacrylates.
Preferably, in the case of thermoplastic polymers, these are polymers, which are derived from unsaturated alcohols and amines or respectively from their acyl or acetal derivatives, such as a polyvinyl alcohol, a poly (acetate, stearate, benzoate or vinyl maleate), a poly (vinyl butyral), a poly (allyl phthalate), a poly (allyl-melamine); as well as their copolymers with the aforementioned olefins.
Preferably, in the case of thermoplastic polymers, they are homo-and copolymers of cyclic ethers, such as poly (alkylene glycols), a poly (ethylene oxide), a poly (propylene oxide) or their copolymers with bis -glycidyl ethers.
Preferably, in the case of polymers, these are thermoplastic polyacetals, such as a poly (oxymethylene), as well as poly (oxymethylenes) containing comonomers, such as eg ethylene oxide; of polyacetals that have been modified with thermoplastic polyurethanes, acrylates or an MBS.
Preferably, in the case of thermoplastic polymers, these are poly (phenylene oxides and sulphides) and mixtures thereof with styrene polymers or polyamides.
Preferably, in the case of thermoplastic polymers, these are polyurethanes, which are derived from polyethers, polyesters and poly (butadiene) with hydroxyl groups located at the ends, on the one hand, and aliphatic or aromatic polyisocyanates, on the other. part, as well as its precursor products.
Preferably, in the case of thermoplastic polymers, these are polyamides and copolyamides, which are derived from diamines and dicarboxylic acids and / or amino carboxylic acids or the corresponding lactams, such as a polyamide 4, a polyamide 6 (® Akulon K122, DSM; ® Zytel 7301, from DuPont; ® Durethan B 29, from Bayer), a 6/6 polyamide (® Zytel 101, from DuPont; ® Durethan A30, ® Durethan Akv, ® Durethan AM, from Bayer; ®Ultramid A3, from the BASF entity) 6/10, 6/9, 6/12, 4/6, 12/12, a polyamide 11, a polyamide 12 (® Grillamid L20, from the Ems Chemie entity), aromatic polyamides starting from m-xylene, a diamine and adipic acid; polyamides, prepared from hexamethylene diamine and iso-and / or terephthalic acids and possibly an elastomer as a modifying agent, e.g. a poly (2,4,4-trimethyl-hexamethylene terephthalamide) or a poly (m-phenylene isophthalamide), block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or elastomers chemically or grafted; or with polyethers, such as with a poly (ethylene glycol), a poly (propylene glycol) or a poly (tetramethylene glycol). In addition, they are polyamides or copolyamides modified with an EPDM or an ABS; as well as condensed polyamides during processing ("polyamide systems for RIM").
Preferably, in the case of polymers, these are polyureas, polyimides, poly (amide imides), poly (etherimides), poly (ester imides), poly (hydantoins) and poly (benzimidazoles).
Preferably, in the case of thermoplastic polymers, these are polyesters, which are derived from dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones, such as a polyethylene terephthalate, a poly (terephthalate) of butylene) (®Celanex 2500, ®Celanex 2002, from Celanese; ®Ultradur, from the BASF entity), a poly (1,4-dimethylol-cyclohexane terephthalate), poly (hydroxybenzoates), as well as block poly (ether esters), which are derived from polyethers with hydroxyl groups located at the ends; and in addition to polyesters modified with polycarbonates or with an MBS.
Preferably, in the case of thermoplastic polymers, these are polycarbonates and poly (ester carbonates), and polysulfones, poly (ether sulphones) and poly (ether ketones).
Preferably, in the case of polymers, these are prepared mixtures (in English polyblends) of the aforementioned polymers, such as e.g. those of a PP and an EPDM, those of a polyamide and an EPDM or ABS, those of a PVC and an EVA, those of a PVC and an ABS, those of a PVC and an MBS, those of a PC and an ABS, those of a PBTP and an ABS, those of a PC and an ASA, those of a PC and a PBT, those of a PVC and a CPE, those of a PVC and acrylates, those of a POM and a thermoplastic PUR, those of a PC and a thermoplastic PUR, those of a POM and an acrylate, those of a POM and an MBS, those of a PPO and a HIPS, those of a PPO and a PA 6.6 and their copolymers, those of a PA and an HDPE, those of a PA and a PP, those of a PA and a PPO, those of a PBT, a PC and an ABS or those of a PBT, a PET and a PC.
The use of phosphonic acids according to the invention and / or their salts is preferred for the production of molded bodies, films, threads and fibers of flame retardant polymers.
Preferably, molded bodies, films, threads and fibers of flame retardant polymers contain from 0.5 to 45% by weight of the phosphinic acid according to the invention and / or its salts, from 0.5 to 95 % by weight of the thermoplastic polymer or mixtures thereof.
Preferably, molded bodies, films, threads and fibers of flame retardant polymers contain from 0.5 to 45% by weight of the phosphinic acid according to the invention and / or its salts, from 0.5 to 95 % by weight of a thermoplastic polymer or mixtures thereof, from 0.5 to 55% by weight of additives and from 0.5 to 55% by weight of a filler material or respectively of reinforcing materials.
The invention also finally relates to a process for the production of flame-retardant polymeric molded bodies, which is characterized in that flame-retardant polymeric molding masses according to the invention are made by injection molding (eg. in an injection molding machine (of the Aarburg Allrounder type) and pressing, injection molding and foaming, injection molding with internal gas pressure, blow molding, sheet casting molding, calendering, stratification or coating at elevated temperatures to give the polymer molded body and gnifugado.
The process for the production of flame retardant polymeric molded bodies is characterized in that the flame retardant polymeric molding mass according to the invention is made at temperatures of the mass according to the invention to give polymeric molded bodies.
Mass temperatures, which are preferred according to the invention, in the case of a polystyrene are from 200 to 250 ° C, in the case of a polypropylene they are from 200 to 300 ° C, in the case of a poly (ethylene terephthalate) (PET) are from 250 to 290 ºC, in the case of a poly (butylene terephthalate) (PBT) they are from 230 to 270 ºC, in the case of a polyamide 6 (PA 6) they are from 260 to 290 ºC, in the case of a polyamide 6.6 (PA 6.6) is 260 to 290 ° C and in the case of a polycarbonate they are 280 to 320 ° C.
A non-flammable thermosetting mass according to the invention is composed of 0.1 to 45% by weight of the phosphinic acid according to the invention, 40 to 90% by weight of an unsaturated polyester and 10 to 60% by weight of a vinyl monomer.
Preferably, in the case of thermostable polymers, these are unsaturated polyester resins, which are derived from copolyesters of saturated and unsaturated dicarboxylic acids or their anhydrides with plurivalent alcohols, as well as vinyl compounds as crosslinking agents. UP resins are hardened by radical polymerization with initiating agents (eg peroxides) and accelerating agents.
Preferred unsaturated dicarboxylic acids and derivatives thereof for the preparation of polyesters are maleic acid anhydride and fumaric acid.
Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and adipic acid.
Preferred diols are 1,2-propanediol, ethylene glycol, di (ethylene glycol), neopentyl glycol and ethoxylated or propoxylated bisphenol A.
A preferred vinyl compound for crosslinking is styrene.
Preferred hardening agent systems are peroxides and concomitant metal initiating agents eg hydroperoxides and cobalt octanoate and / or benzoyl peroxide and aromatic amines and / or UV light (ultraviolet) and photosensitizing agents eg benzoin ethers.
Preferred hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethyl hexanoate, tert-butyl permaleate, tert perisobutyrate .-Butyl, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide or dicyclohexyl peroxide dicarbonate.
Preferably, the initiating agents are used in proportions of 0.1 to 20% by weight, more preferably 0.1 to 15% by weight, calculated on the basis of the mass of all comonomers.
Preferred metal concomitant initiating agents are compounds of cobalt, manganese, iron, vanadium, nickel or lead. Preferably, the concomitant metal initiating agents are used in proportions of 0.05 to 1% by weight, calculated on the basis of the mass of all comonomers.
Preferred aromatic amines are dimethyl-aniline, dimethyl-p-toluene, diethyl-aniline and phenyl-diethanolamines.
A process for the production of flame retardant copolymers is performed in such a way that at least one ethylenically unsaturated dicarboxylic acid anhydride is copolymerized, which is derived from at least one C4-C8 dicarboxylic acid, (B) at least less a vinyl aromatic compound and (C) a polyol, and then (D) are reacted with a phosphinic acid according to the invention.
A process for the production of non-flammable thermosetting masses is carried out in such a way that a thermosetting resin is mixed with a flame retardant agent component based on a phosphinic acid according to the invention, and the resulting mixture is wet pressed (cold pressed) at about pressures of 3 to 10 bars and at temperatures of 20 to 60 ° C.
Another process for the production of non-flammable thermosetting masses is carried out in such a way that a thermosetting resin is mixed with a phosphinic acid according to the invention and the resulting mixture is wet pressed at pressures of 3 to 10 bars and at temperatures of 80 to 150 ºC (hot pressed or tempered temperature).
Preferably, in the case of polymers, they are cross-linked epoxy resins, which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, eg bisphenol-A-diglycidyl ethers, bisphenol-F-diglycidyl products -ethers, which are crosslinked by means of usual hardening and / or accelerating agents.
Glycidyl compounds usable according to the invention are diglycidyl esters of bisphenol-A, diglycidyl esters of bisphenol F, poly (glycidyl esters) of phenol and formaldehyde resins and cresol and formaldehyde resins, polyglycidyl esters of phthalic, isophthalic and tephthalic acid , as well as trimellitic acid, N-glycidyl compounds of aromatic amines and heterocyclic nitrogen bases, as well as di- and polyglycidyl compounds of plurivalent aliphatic alcohols.
Suitable hardening agents are polyamines such as diethylene triamine, triethylene tetraamine, aminoethyl piperazine, isophorone diamine, a poly (amidoamine), diamino diphenyl methane, diamino diphenol sulfones and dicyandiamide.
Suitable hardening agents are pluribasic acids or their anhydrides such as, for example, phthalic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride and methyl hydroxyacrylic acid anhydride.
Suitable hardening agents are phenols such as e.g. a phenol and novolac resin, a cresol and novolac resin, a resin of a dicyclopentadiene and phenol adduct, a phenol and aralkyl resin, a cresol and aralkyl resin, a naphthol and aralkyl resin, a phenol resin and aralkyl modified with biphenol, a phenol and trimethylolmethane resin, a tetraphenylethane resin, a naphthol and novolac resin, a concomitant resin of naphthol and phenol condensate, a resin of a concomitant condensate of naphthol and cresol, a phenolic resin modified with biphenol and a phenolic resin modified with aminotriazine.
These hardening agents can be used alone or in combination with each other.
Catalysts or accelerating agents according to the invention to perform cross-linking in the case of polymerization, are tertiary amines, benzyl dimethyl amine, N-alkyl pyridines, imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 2- ethyl-4-methyl-imidazole, 2-ethyl-4-methyl-imidazole, 2-phenyl-imidazole, 2-heptadecyl-imidazole, metal salts of organic acids, Lewis acids and salts of complex compounds with amines.
Epoxy resins are suitable for filler with putty of electrical or respectively electronic construction pieces and for wetting and impregnation processes. In electrical engineering, the epoxy resins used are predominantly non-flammable and are used for printed circuit boards and insulators.
Preferably, in the case of polymers, they are cross-linked polymers, which are derived from aldehydes, on the one hand, and phenols, urea or melamine, on the other hand, such as phenol and formaldehyde, urea and formaldehyde and melamine and formaldehyde.
Preferably, in the case of polymers, they are crosslinkable acrylic resins, which are derived from substituted esters of acrylic acid, such as eg epoxyacrylates, urethane acrylates or polyester acrylates.
Preferably, in the case of polymers, they are alkyd resins, polyester resins and acrylate resins, which are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates
or epoxy resins.
A flame retardant polyurethane molding mass can be produced by reacting 0.1 to 50 parts by weight of a phosphinic acid according to the invention with 30 to 65 parts by weight of a polyisocyanate and with 30 to 65 parts by weight of a polyol.
A process for the production of a flame retardant polyurethane molding mass is characterized in that from 170 to 70 parts by weight, preferably from 130 to 80 parts by weight, of polyisocyanates according to the invention with 100 parts by weight are reacted of a polyol according to the invention, from 0.1 to 50 parts by weight of a phosphinic acid according to the invention and from 0.1 to 4 parts by weight, particularly preferably from 1 to 2 parts by weight, of a catalyst according to the invention, and optionally foamed with 0.1 to 1.8 parts by weight, preferably 0.3 to 1.6 parts by weight, of an expanding agent.
Preferred polyols are adducts with ethylene glycol alkylene oxides, 1,2-propanediol, bisphenol A, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sugars, degraded starches, ethylene diamine, diaminotoluene and / or aniline, which serve as an initiating agent. Preferred oxyalkylation agents according to the invention preferably contain from 2 to 4 carbon atoms, especially preferably they are ethylene oxide and propylene oxide.
Preferred polyester polyols are obtained by polycondensation of a polyalcohol such as ethylene glycol, di (ethylene glycol), propylene glycol, 1,4-butanediol, 1,5-pentanediol, methyl-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol , diglycerol, glucose and / or sorbitol, with a dibasic acid such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid and terephthalic acid. These polyester polyols can be used alone or in combination.
Suitable polyisocyanates are aromatic, alicyclic or aliphatic polyisocyanates, which have no less than two isocyanate groups and mixtures thereof. Aromatic polyisocyanates such as tolyl diisocyanate, methylenediphenyl diisocyanate, naphthylene diisocyanates, xylethylene diisocyanate, tris (4-isocyanate phenyl) methane and polymethylene polyphenylene diisocyanates are preferred; alicyclic polyisocyanates are methylene diphenyl diisocyanate, tolyl diisocyanate; and aliphatic polyisocyanates are hexamethylene diisocyanate, isophoren diisocyanate, demeryl diisocyanate, a mixture of 1,1-methylene bis (4-isocyanate-cyclohexane-4,4'-diisocyanate-dicyclohexylmethane), 1,4-cyclohexyl- diisocyanate, types (R) Desmodur (from Bayer) and lysine diisocyanate, and mixtures thereof.
Suitable polyisocyanates are modified products, which are obtained by reacting a polyisocyanate with a polyol, urea, carbodiimide and / or biuret.
Suitable catalysts are strong bases, alkali metal salts of carboxylic acids or aliphatic tertiary amines. Quaternary ammonium hydroxides, an alkali metal hydroxide or alkoxide, sodium or potassium acetate, potassium octoate, sodium benzoate, 1,4-diazabicyclo [2.2.2] octane, N, N, N ', N are preferred '-tetramethylhexamethylene diamine, N, N, N', N'-tetramethyl-propylenediamine, N, N, N ', N', N '' - pentamethyl-diethylenetriamine, N, N'-di- (C1- alkyl C2) -piperazine, trimethylaminoethyl-piperazine, N, N-dimethyl-cyclohexylamine, N, N-dimethyl-benzylamine, N-methylmorpholine, N-ethyl-morpholine, trimethylamine, triethylamine, tributylamine, triethylene diamine, bis (dimethylaminoalkyl) piperazines, N, N, N ', N'-tetramethyl-ethylenediamine, N, N-diethyl-benzylamine, bis (N, N-diethylaminoethyl) adipate, N, N, N', N'tetramethyl-1,3-butanediamine, N, N-diethyl- [beta] -phenylethylamine, 1,2-dimethyl-imidazole, 2-methyl-imidazole, etc.
The weight ratio between the polyisocyanate and the polyol is preferred, which is preferably 170 by 70 and more preferably 130 by 80, based on 100 parts by weight of the polyol.
The weight ratio of the catalyst of 0.1 to 4 parts by weight, particularly preferably 1 to 2 parts by weight, based on 100 parts by weight of the polyol is preferred.
Preferred blowing agents are water, a hydrocarbon, a fluorochlorinated hydrocarbon, a fluorinated hydrocarbon, etc.
The amount of a swelling agent optionally employed is 0.1 to 1.8 parts by weight, preferably 0.3 to 1.6 parts by weight, more preferably 0.8 to 1.6 parts. by weight, based on 100 parts by weight of the polyol.
The decomposition temperature is determined according to classical thermogravimetric procedures. In this case, the decomposition temperature is defined as the temperature at which a 2% weight loss occurs.
Chemical agents used: HP (O) (OFe1 / 3) -CH2-CH2-P (O) (OFe1 / 3) -H
<dl><dt>HMEPPS: </dt><dd>1-hydroxy-1-methyl-phosphonic acid</dd></dl>
<dl><dt> HP (O) (OH) C (CH3) 2OH </dt><dd /></dl>
<dl><dt>Wako V 65 B </dt><dd>2,2'-azobis-2,4-dimethyl-valeronitrile </dd></dl>
<dl><dt>Waco V50: </dt><dd>2,2'-azobis-2-amidinopropane hydrochloride </dd></dl>
<dl><dt>VAZO 52: </dt><dd>2,2'-azobisisopropylbutyronitrile </dd></dl>
<dl><dt>VAZO 67: </dt><dd>2,2'-azobismethylbutyronitrile </dd></dl>
<dl><dt>VAZO 64: </dt><dd>AIBN 2,2'-azobisisobutyronitrile </dd></dl>
<dl><dt>EBHS: </dt><dd> ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinic acid, </dd></dl>
<dl><dt> HO-C (CH3) 2-P (O) (OH) -CH2-CH2-P (O) (OH) -C (CH3) 2-OH </dt><dd /></dl>
<dl><dt>EBHNa: </dt><dd>ethylene-bis- (1-hydroxy-1-methylethyl) -phosphonate disodium,</dd></dl>
<dl><dt> HO-C (CH3) 2-P (O) (ONa) -CH2-CH2-P (O) (ONa) -C (CH3) 2-OH, </dt><dd /></dl>
<dl><dt>EBHA1:</dt><dd> ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate aluminum, </dd></dl>
<dl><dt>HO-C (CH3) 2-P (O) (OAl1 / 3) -CH2-CH2-P (O) (OAl1 / 3) -C (CH3) 2-OH, </dt><dd /></dl>
<dl><dt>EBHZn: </dt><dd>ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate zinc, </dd></dl>
<dl><dt>HO-C (CH3) 2-P (O) (OZn1 / 2) -CH2-CH2-P (O) (OZn1 / 2) -C (CH3) 2-OH, </dt><dd /></dl>
<dl><dt>EBHCa: </dt><dd>ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate calcium, </dd></dl>
<dl><dt>HO-C (CH3) 2-P (O) (OCa1 / 2) -CH2-CH2-P (O) (OCa1 / 2) -C (CH3) 2-OH, </dt><dd /></dl>
<dl><dt>EBHMg: </dt><dd>ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate magnesium, </dd></dl>
<dl><dt>HO-C (CH3) 2-P (O) (OMg1 / 2) -CH2-CH2-P (O) (OMg1 / 2) -C (CH3) 2-OH, </dt><dd /></dl>
<dl><dt>EBHFe: </dt><dd>ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate iron, </dd></dl>
<dl><dt>HO-C (CH3) 2-P (O) (OFe1 / 3) -CH2-CH2-P (O) (OFe1 / 3) -C (CH3) 2-OH, </dt><dd /></dl>
<dl><dt>EBPS: </dt><dd>ethylene bisphosphinic acid, </dd></dl>
<dl><dt>HP (O) (OH) -CH2-CH2-P (O) (OH) -H </dt><dd /></dl>
<dl><dt>EBPNa:</dt><dd> disodium ethylene bisphosphinate, </dd></dl>
<dl><dt>HP (O) (ONa) -CH2-CH2-P (O) (ONa) -H </dt><dd /></dl>
<dl><dt>EBPA1: </dt><dd>ethylene aluminum bisphosphinate </dd></dl>
<dl><dt>HP (O) (OAl1 / 3) -CH2-CH2-P (O) (OAl1 / 3) -H </dt><dd /></dl>
<dl><dt>EBPZn: </dt><dd>zinc ethylene bisphosphinate, </dd></dl>
<dl><dt>HP (O) (OZn1 / 2) -CH2-CH2-P (O) (OZn1 / 2) -H </dt><dd /></dl>
<dl><dt>EBPCa:</dt><dd> ethylene calcium bisphosphinate, </dd></dl>
<dl><dt>HP (O) (OCa1 / 2) -CH2-CH2-P (O) (OCa1 / 2) -H </dt><dd /></dl>
<dl><dt>EBPFe: </dt><dd>ethylene iron bisphosphinate </dd></dl>
EBPMel: ethylene melamine bisphosphinate HP (O) (OC3H6N6) -CH2-CH2-P (O) (OC3H6N6) -H
Polystyrene: Polystyrene 143 E, from BASF
5 Pa 6.6: ® Ultramid A3, of the BASF entity MPP: ®Melapur 200/70, of the entity Ciba SC Glass fibers 1: VPPG 3540, from PPG Industries, Inc Glass fibers 2: ® Vetrotex EC 10983, from Saint Gobain
Examples
10 Preparation of concentrated hypophosphorous acid (HPS, H3PO2)
A concentrated HPS can be prepared according to the state of the art. In this case, a commercially available 50% aqueous hypophosphorous acid is concentrated by evaporation concentration until the weight is recorded on a rotary evaporator in the vacuum of a water tube and at a temperature not exceeding 40 ° C.
fifteen ? 1-Hydroxy-1-Methyl-Phosphine Acid (HMEPPS)
The 1-hydroxy-1-methyl ethyl phosphine acid is prepared according to the state of the art from a concentrated HPS and is isolated from as a pale yellow oil to as a white resin in a yield of 96 %.
Preparation prescription for ethylene-bis- (1-hydroxy-1-methyl ethyl phosphine)
twenty In a five-mouth flask with a capacity of two liters, equipped with a stirring mechanism, a thermometer, an intense coolant, a dosing device of the initiating agent, a frit for the introduction of acetylene and a nitrogen coating, were previously arranged HMEPPS and amyl alcohol and homogenized. In this case the reaction mixture was heated. The stirring speed was 460 rpm (revolutions per minute). After the reaction temperature had been reached, the initiating agent was added in dosage form
25 of a 10% solution in the corresponding solvent by means of a pump. Acetylene was introduced with a flow rate of 5-6 l / h. The product precipitated in the course of the reaction, and, after completion of the reaction, was filtered through a suction filter, and washed twice with acetone. The powder was dried in a drying oven at 120 ° C. Typical purity: 93.6% (according to 31P-NMR). The product is crystalline according to X-rays. The following reflexes are observed (CuKalfa1 1,54056 Ang radiation): Relative intensity / d value; 20.2, 7,78620; 62.9,
30 5,63264; 100.0, 5.33438; 27.5, 4.91046; 47.2%, 4,49822 Ang. The hydroxyl group index is 290 mg of KOH / g.
Optionally, the product can be digested with ethanol to perform further purification (25% dispersion). The yields in the case of this stage are 80-90% and lead to purities of 99.2% (according to 31P-NMR).
Example 1
From 345 g of the 1-hydroxy-1-methyl ethyl phosphic acid, with 29.8 g of the starting agent Wako V65 B in total in 803 35 g of amyl alcohol, at 80 ° C for 11 h, 210 g are obtained of the product.
Example 2
From 345 g of 1-hydroxy-1-methyl ethyl phosphic acid, with 18.3 g of the Wako 52 starter agent in total in 803 g of amyl alcohol, at 50 ° C for 11 h, 141 g of the product are obtained .
Example 3
40 From 345 g of the 1-hydroxy-1-methyl ethyl phosphic acid, with 19.7 g of the total AIBN initiating agent in 803 g of amyl alcohol, at 120 ° C for 8 h, 240 g of the product are obtained.
Example 4
From 345 g of 1-hydroxy-1-methyl ethyl phosphic acid, with 6.9 g of the Wako V65 B starter agent in total in 803 g of amyl alcohol, at 80 ° C for 32 h, 187 g of the product.
Four. Five Example 5
From 345 g of the 1-hydroxy-1-methyl ethyl phosphic acid, with 29.8 g of the Wako V65 B starting agent in total in 350 g of amyl alcohol, at 80 ° C, for 11 h, 259 g of the product.
Example 6
(Ethylene-bis- (1-hydroxy-1-methylethyl phosphinate) disodium)
In a beaker with a capacity of 1 l, 141 g of demineralized water are pre-arranged and with stirring, 40 g of NaOH flakes are added with caution, then 137.1 g of EBHS. 318 g of a 50% by weight solution of EBHNa are obtained.
General prescription for the preparation of ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinates salts and of ethylene bisphosphinate salts
In a six-mouth flask with a capacity of two liters or four liters respectively (equipped with a stirring mechanism, a thermometer, a plug, an introduction tube and a reflux coolant) or the demineralized water and metal salt is dissolved by heating at the precipitation temperature, or the finished solution of the metal salt is previously arranged and heated to the precipitation temperature. Through an introduction tube, with the help of a pump, the calculated amount of EBHNa solution is provided by pumping over a pre-established period of time. The previously chosen precipitation temperature is maintained in this case, and it is stirred at a previously chosen agitation speed. The solid product is separated by hot filtration through a suction filter, after this it is dispersed with demineralized water at 90 ° C (in the fivefold amount of theoretical yield) and again filtered hot through a filter suction. The solid material is dried for 15 h in the drying oven at 100 ° C and at 30 mbar.
Example 7
(Ethylene-bis- (1-hydroxy-1-methyl ethyl) -phosphinate aluminum)
According to the general prescription for the preparation of ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinates of metals, 318 g of an EBHNa solution are reacted with 209 g of an aluminum sulfate solution for 2 ha 90 ° C and with a stirring speed of 750 rpm. 132 g of a solid product are obtained. The product is crystalline according to X-rays. The following reflexes are observed (CuKalfa1 1,54056 Ang radiation): Relative intensity / d value; 65.6, 11.03554; 100.0, 10.55511; 30.2, 8.91804; 33.4%, 8.74638 Ang. The analysis data are shown in Table 2.
Example 8
(Ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate zinc)
According to the general prescription for the preparation of ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinates of metals, 318 g of an EBHNa solution are reacted with 144 g of zinc sulfate heptahydrate, which are dissolved in
1,240 g of demineralized water, for 2 h at 90 ° C and with a stirring speed of 250 rpm. 135 g of a solid product are obtained. The product is crystalline according to X-rays. The following reflections are observed (CuKalfa1 1,54056 Ang radiation): Relative intensity / d value; 100.0, 11.09087; 35.7, 10.67607; 29.4, 5,26978; 40.3%, 4,91046 Ang. The analysis data are shown in Table 2.
Example 9
(Ethylene-bis- (1-hydroxy-1-methyl ethyl) -phosphinate magnesium)
According to the general prescription for the preparation of ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinates of metals, 318 g of an EBHNa solution are reacted with 102 g of magnesium chloride hexahydrate, which are dissolved in 568 g of demineralized water, for 2 h at 50 ° C and with a stirring speed of 750 rpm. 111 g of a solid product are obtained. The product is crystalline according to X-rays. The following reflexes are observed (CuKalfa1 1,54056 Ang radiation): Relative intensity / d value; 11,23166 Ang. The analysis data are shown in Table 2.
Example 10
(Ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinate iron)
According to the general prescription for the preparation of ethylene-bis- (1-hydroxy-1-methylethyl) -phosphinates of metals, 318 g of an EBHNa solution is reacted with 67 g of iron sulfate, which are dissolved in 2,710 g of demineralized water, for 8 h at 90 ° C and with a stirring speed of 750 rpm. 139 g of a solid product are obtained. The product is crystalline according to the X-rays. The analysis data are shown in Table 2.
Example 11
Prescription for the preparation of an ethylene-bisphosphinic acid by separation of acetone from an ethylene-bis- (1-hydroxy-1-methyl-phosphonic acid)
In a four-mouth flask, equipped with a distillation quadrilateral, a drip funnel and a thermometer, 274 g of EBHS are weighed and introduced and mixed with 4 moles of hydrochloric acid (37%). The equipment is inertized with nitrogen. It is heated with an oil bath to the boiling point of hydrochloric acid and the solution is boiled at reflux (head temperature 105-108 ° C). By separating acetone, the head temperature decreases over time. Again and again a distilled material is discharged until the head temperature remains constant at 108 ° C (in the meantime it is refilled by means of a drip funnel with 37% hydrochloric acid). If the boiling point has been reached, the remaining hydrochloric acid is distilled off with a rotary evaporator at 1 mbar and at a maximum of 110 ° C.
Example 12
(Disodium ethylene bisphosphinate)
In a beaker with a capacity of 1 l, 83 g of demineralized water are pre-arranged with stirring and 40 g of NaOH flakes are added with caution, and then 79 g of EBPS are added. 202 g of a 50% by weight solution of EBPNa are obtained.
Example 13
(Aluminum ethylene bisphosphinate)
According to the general prescription for the preparation of the metal ethylene bisphosphinates, 202 g of an EBPNa solution are reacted with 209 g of an aluminum sulfate solution for 2 h at 90 ° C and with a stirring speed of 750 rpm. 71 g of a solid product are obtained. The analysis data are shown in Table 3.
Example 14
(Zinc ethylene bisphosphinate)
According to the general prescription for the preparation of ethylene metal bisphosphinates, 202 g of an EBPNa solution are reacted with 144 g of a zinc sulfate heptahydrate solution, which is dissolved in 770 g of demineralized water, for 1 ha 100 ° C and with a stirring speed of 1,500 rpm. 95 g of a solid product are obtained. The product is crystalline according to X-rays. The following reflexes are observed (CuKalfa1 1,54056 Ang radiation): Relative intensity / d value; 39.2, 7.82398; 37.2, 6.52943; 100.0, 3,909381; 63.3%, 3.22809 Ang. The analysis data are shown in Table 3.
Example 15
(Calcium ethylene bisphosphinate)
According to the general prescription for the preparation of the metal ethylene bisphosphinates, 202 g of an EBPNa solution are reacted with 74 g of calcium chloride dihydrate, which are dissolved in 380 g of demineralized water, for 2 h at 90 ° C and with a stirring speed of 750 rpm. 58 g of a solid product are obtained. The analysis data are shown in Table 3.
Example 16
(Ethylene iron bisphosphinate)
According to the general prescription for the preparation of the metal ethylene bisphosphinates, 202 g of the EBPNa solution are reacted with 67 g of iron sulfate, which are dissolved in 2,720 g of demineralized water, for 2 h at 90 ° C and with a stirring speed of 750 rpm. 90 g of a solid product are obtained. The analysis data are shown in Table 3.
Example 17
(Ethylene dimethyl amine bisphosphinate)
Hot, 79 g of EBPS and 126 g of melamine are dissolved in ethylene glycol. Upon cooling, 148 g of a solid product precipitate. The product is crystalline according to the X-rays. The following reflexes are observed (CuKalfa1 1,54056 Ang radiation): Relative intensity / d value; 39.0, 5,71392; 40.2, 3.95093; 100.0%, 3,43265 Ang. The analysis data are shown in Table 3.
Example 18
(Comparative) According to the general prescription, a mixture of 70% by weight of a polystyrene and 30% by weight of calcium hypophosphite is formulated in a twin screw extruder at 170 ° C to give a flame retardant polymer molding mass. An inflammation appears by decomposition of the flame retardant agent during processing.
Example 19
According to the general prescription, a mixture of 70% by weight of a polystyrene and 30% by weight of the product of Example 12 is formulated in a twin screw extruder at 170 ° C to give a flame retardant polymer molding mass. After drying, the molding masses are made in an injection molding machine at 200 to 250 ° C to give flame retardant polymeric molded bodies and a classification is determined according to UL-94 of V-0.
Example 20
According to the general prescription, a mixture of 70% by weight of a polystyrene and 30% by weight of the product of Example 13 is formulated in a twin screw extruder at 170 ° C to give a flame retardant polymer molding mass. After drying, the molding masses are made in an injection molding machine at 200 to 250 ° C to give flame retardant polymeric molded bodies and a classification is determined according to UL-94 of V-0.
Example 21
According to the general prescription, a mixture of 70% by weight of a polystyrene and 30% by weight of the product of Example 14 is formulated in a twin screw extruder at 170 ° C to give a flame retardant polymer molding mass. After drying, the flame retardant molding mass is made in an injection molding machine at 200 to 250 ° C to give flame retardant polymeric molded bodies and a classification is determined according to UL-94 of V-0.
Example 22
According to the general prescription, a mixture of 70% by weight of a polystyrene and 30% by weight of the product of Example 15 is formulated in a twin screw extruder at 170 ° C to give a flame retardant polymer molding mass. After drying, the molding masses are made in an injection molding machine at 200 to 250 ° C to give flame retardant polymeric molded bodies and a classification is determined according to UL-94 of V-0.
Example 23
According to the general prescription, a mixture of 50% by weight of a PA 6.6, 12.5% by weight of the product of Example 12, 12.5% by weight of MPP and 25% by weight of glass fibers is formulated in a twin screw extruder at 260 to 280 ° C to give a flame retardant polymer molding mass. After drying, the flame retardant molding mass is made in an injection molding machine at 260 to 290 ° C to give flame retardant polymeric molded bodies and a classification is determined according to UL-94 of V-1.
Example 24
According to the general prescription, a mixture of 50% by weight of a PBT, 12.5% by weight of the product of Example 13, 12.5% by weight of MPP and 25% by weight of glass fibers is formulated in a twin screw extruder at 230 to 260 ° C to give a flame retardant polymer molding mass. After drying, the flame retardant molding mass is made in an injection molding machine at 230 to 270 ° C to give flame retardant polymeric molded bodies and a classification is determined according to UL-94 of V-1.
Example 25 (comparative)
An adhesive mass of 82% of Airflex 920 (from Air Products and Chemicals Inc), 1% of Tego antifoam agent (from East Falls Corp.), 15% of AP 422 (from Clariant GmbH) and of 2% of Alcogum 296W (from ALCO Chemical). 100 g of this dough are weighed and placed in a threaded wide mouth bottle with a capacity of 250 ml and stored for 8 h at 60 ° C. With the formaldehyde test sticks of the Dräger Sicherheitstechnik GmbH (type 0.2 / a), the gas enclosure is investigated after storage. After pumping ten times, a concentration of formaldehyde greater than 50 ppm is read.
Example 26
An adhesive mass of 80% is produced based on Airflex 920 (from Air Products and Chemicals Inc), 1% from Tego antifoam agent (from East Falls Corp.), 15% from AP 422 (from Clariant GmbH), from 2% Alcogum 296W (from ALCO Chemical) and 2% of the product from Example 11. The product is tested as described in Example 25. A concentration of formaldehyde greater than 10 ppm is read. The glue is suitable especially for construction uses.
Table 1: Preparation of ethylene bis- (1-hydroxy-2-methyl ethyl phosphine)
<dl><dt>Example </dt><dd>HPSg Adduct Type G initiating agent Type G solvent Acetylene g TºC th Product g% ZT ºC, 2% of GV 31 P-NMR</dd></dl>
<dl><dt>ppm </dt><dd /></dl>
<dl><dt>1 </dt><dd>3. 4. 5 Wako V65 B 29.8 AmOH 803 64 80 eleven 210 55 167 54.8 </dd></dl>
<dl><dt>2 </dt><dd>3. 4. 5 VAZO 52 18.3 AmOH 803 64 fifty eleven 141 37 </dd></dl>
<dl><dt>3 </dt><dd>3. 4. 5 AIBN 19.7 OctOH 803 64 120 8 240 63 </dd></dl>
<dl><dt>4 </dt><dd>3. 4. 5 Wako V65 B 6.9 AmOH 803 64 80 32 187 49 </dd></dl>
<dl><dt>5 </dt><dd>3. 4. 5 Wako V65 B 29.8 AmOH 350 64 80 eleven 259 68 </dd></dl>
GV = weight loss ZT = decomposition temperature
Table 2: Preparation of ethylene bis- (1-hydroxy-1-methyl ethyl phosphinates) salts
<dl><dt>Example </dt><dd>Educto A g Educto BG Solvent g th TºC Rpm agitation speed Product g ZT ºC, 2% of GV 31 P-RMNppm Content of P exp. % teo. %</dd></dl>
<dl><dt>6 </dt><dd>EBHS 137 NaOH 40 H2 O 141 0.5 30 300 318 - 46 - -</dd></dl>
<dl><dt>7 </dt><dd>EBHNa 318 solution of Al2 (SO4) 34.3% of Al 209 H2 O 0 two 90 750 132 248 46 20.6 21.4 </dd></dl>
<dl><dt>8 </dt><dd>EBHNa 318 ZnSO4 * 7aq 144 H2 O 1,240 two 90 250 135 283 46 17.9 18.4 </dd></dl>
<dl><dt>9 </dt><dd>EBHNa 318 MgCl2 * 6aq 102 H2 O 568 two fifty 750 111 260 46 19.8 20.9 </dd></dl>
<dl><dt>10 </dt><dd>EBHNa 318 Fe2 (SO4) 3 67 H2 O 2,710 8 90 750 139 262 46 19.5 twenty </dd></dl>
Table 3: Preparation of ethylene bisphosphinate salts
<dl><dt>Example </dt><dd>Educto AG Educto BG Solvent g th TºC Agitation speed Rpm Product g ZT ºC, 2% of GV 31 P-RMNppm Content of P exp. % teo. %</dd></dl>
<dl><dt>12 </dt><dd>EBPS 79 NaOH 40 H2 O 83 0.5 30 300 202 - 31 - -</dd></dl>
<dl><dt>13 </dt><dd>EBPNa 202 solution of Al2 (SO4) 34.3% of Al 209 H2 O 0 two 90 750 71 > 600 31 33.2 35.6 </dd></dl>
<dl><dt>14 </dt><dd>EBPNa 202 ZnSO4 * 7aq 144 H2 O 770 1 100 1,500 95 > 1,000 31 27.7 28.0 </dd></dl>
<dl><dt>15 </dt><dd>EBPNa 202 CaCl2 * 2aq 74 H2 O 380 two 90 750 58 > 600 31 30.0 31.6 </dd></dl>
<dl><dt>16 </dt><dd>EBPNa 202 Fe2 (SO4) 3 67 H2 O 2,720 two 90 750 90 > 600 31 29.9 32.1 </dd></dl>
<dl><dt>17 </dt><dd>EBPS 79 melamine 126 ethylene glycol 3,900 two 100 750 148 279 31 14.9 15.1 </dd></dl>
Table 4: Flame retardant polymer molding masses and flame retardant tests on flame retardant polymeric molded bodies
<dl><dt>Examples </dt><dd> 18 19 20 21 22 </dd></dl>
<dl><dt>Polystyrene </dt><dd>[% in weigh] 70 70 70 70 70 </dd></dl>
<dl><dt>Calcium hypophosphite </dt><dd>[% in weigh] 30 </dd></dl>
<dl><dt>Product of Example 13 </dt><dd>[% in weigh] 30 </dd></dl>
<dl><dt>Product of Example 14 </dt><dd>[% in weigh] 30 </dd></dl>
<dl><dt>Product of Example 15 </dt><dd>[% in weigh] 30 </dd></dl>
<dl><dt>Product of Example 16 </dt><dd>[% in weigh] 30 </dd></dl>
<dl><dt>Classification according to UL-94 (1.5 mm) </dt><dd>] Inflammation during processing V-0 V-0 V-0 V-0 </dd></dl>
Table 5: Flame retardant polymer molding masses and flame retardant tests on flame retardant polymeric molded bodies
<dl><dt>Examples </dt><dd> 23 24 </dd></dl>
<dl><dt>[% in weigh] </dt><dd /><dt>[% in weigh] </dt><dd /></dl>
<dl><dt>PA 6.6 </dt><dd> 50 </dd></dl>
<dl><dt>PBT </dt><dd> 50 </dd></dl>
<dl><dt>1 glass fibers </dt><dd> 25 </dd></dl>
<dl><dt>Fiberglass 2 </dt><dd> 25 </dd></dl>
<dl><dt>Product of Example 13 </dt><dd> 12,5 </dd></dl>
<dl><dt>Product of Example 14 </dt><dd> 12,5 </dd></dl>
<dl><dt>MPP </dt><dd> 12,5 - </dd></dl>
<dl><dt>MC </dt><dd> - 12,5 </dd></dl>
<dl><dt>Class according to UL-94 </dt><dd>V-1 V-1</dd></dl>
Contents8
12 members in 7 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 102006048698 | Germany | A | |
| 102006048698 | Germany | – | |
| 2007008692 | European Patent Office (EPO) | W |
Members12
| Document | Office | Kind | |
|---|---|---|---|
| DE102006048698A1 | Germany | A1 | |
| WO2008043499A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2081942A1 | European Patent Office (EPO) | A1 | |
| JP2010507570A | Japan | A | |
| US2010093239A1 | United States of America | A1 | |
| EP2081942B1 | European Patent Office (EPO) | B1 | |
| AT537180T | Austria | T | |
| ATE537180T1 | Austria | T1 | |
| US8084518B2 | United States of America | B2 | |
| ES2376009T3This record | Spain | T3 | |
| US2012064790A1 | United States of America | A1 | |
| JP5438516B2 | Japan | B2 |
Numbers
- Publication
- 2376009
- Application
- 7818768
Titles2
- Spanish
- ACIDOS ETILENDIFOSFINICOS.
- English
- ETHYDIFOSPHINIC ACIDS.
Classification
- CPC, 15
- C07F9/305
- B27K3/34
- B27K2240/30
- C02F5/14
- C02F2103/10
- C02F2103/16
- C02F2303/08
- C07F9/485
- C08G18/388
- C08G18/40
- C08G2101/00
- C08K5/5313
- C09K21/12
- Y10T442/3976
- Y10T442/2672
- IPC, 1
- C07F9 30