HK1198035A - Mixtures of diphosphinic acids and alkylphosphonic acids, a process for the preparation thereof and the use thereof - Google Patents

Description

Mixtures of diphosphinic acids and alkylphosphonic acids, method for the production thereof, and use thereof

The invention relates to mixtures of at least one diphosphinic acid and at least one alkylphosphonic acid, to a method for the production thereof and to the use thereof.

In the production of printed circuit boards, which are used to an increasing extent in various devices, such as computers, cameras, cell phones, LCD and TFT screens and other electronic instruments, different materials, in particular plastics, are used. This includes, inter alia, thermosets, glass fiber reinforced thermosets and thermoplastics. Epoxy resins are particularly frequently used because of their good properties.

These printed circuit boards must be rendered flame retardant or fire retardant according to the relevant standards (IPC-4101, specifications for rigid and multilayer printed circuit board substrates).

Thermal expansion of printed circuit boards is a problem during their production. The electronic production conditions of printed circuit boards require that the printed circuit boards withstand high thermal loads without being damaged or deformed. The application of the conductor tracks to the printed circuit board (lead-free soldering) is carried out at temperatures of up to about 260 ℃.

It is therefore important that the printed circuit board does not warp under thermal stress and that the product remains dimensionally stable.

Especially even in the case of prepregs ("short for pre-impregnated fibers") and laminates, the thermal expansion is significant because these constitute the original form or precursor of the printed circuit board. Therefore, it is important to minimize the thermal expansion of the test specimen to obtain a good dimensionally stable product (e.g., a finished printed circuit board).

It is an object of the present invention to modify polymers for prepregs, printed circuit boards and laminates such that they undergo only very low thermal expansion (if any) and achieve the necessary dimensional stability.

This object is achieved by a mixture of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II),

wherein:

R¹，R²representation H, C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl radical, C₇-C₁₈An alkylaryl group;

R⁴is represented by C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl radical, C₇-C₁₈An alkylaryl group;

wherein:

R³representation H, C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl and/or C₇-C₁₈An alkylaryl group.

Preferably, R¹、R²And R³Identical or different and denotes H-, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl, and R⁴Represents ethylene, butylene, hexylene or octylene.

Preferably, the mixture comprises from 0.1 to 99.9% by weight of diphosphinic acids of the formula (I) and from 99.9 to 0.1% by weight of alkylphosphonic acids of the formula (II).

Particularly preferably, the mixture comprises from 40 to 99.9% by weight of diphosphinic acids of the formula (I) and from 60 to 0.1% by weight of alkylphosphonic acids of the formula (II). Preference is likewise given to mixtures comprising from 60 to 99.9% by weight of diphosphinic acids of the formula (I) and from 40 to 0.1% by weight of alkylphosphonic acids of the formula (II).

In particular, the mixture comprises from 80 to 99.9% by weight of diphosphinic acids of the formula (I) and from 20 to 0.1% by weight of alkylphosphonic acids of the formula (II).

In another embodiment, the mixture comprises 90 to 99.9% by weight of diphosphinic acids of the formula (I) and 10 to 0.1% by weight of alkylphosphonic acids of the formula (II).

In yet another embodiment, the mixture comprises 95 to 99.9 wt.% of diphosphinic acids of formula (I) and 5 to 0.1 wt.% of alkylphosphonic acids of formula (II).

For many applications, preference is given to mixtures comprising from 98 to 99.9% by weight of diphosphinic acids of the formula (I) and from 2 to 0.1% by weight of alkylphosphonic acids of the formula (II).

For the purposes of the present invention, particular preference is given to mixtures comprising from 98 to 99.9% by weight of ethylene-1, 2-bis (ethylphosphinic acid) and from 2 to 0.1% by weight of ethylphosphonic acid.

The present invention preferably relates to mixtures of the above-mentioned type in which the diphosphinic acid is ethylene-1, 2-bis (ethylphosphinic acid), ethylene-1, 2-bis (propylphosphinic acid), ethylene-1, 2-bis (butylphosphinic acid), ethylene-1, 2-bis (pentylphosphinic acid), ethylene-1, 2-bis (hexylphosphinic acid), butylene-1, 2-bis (ethylphosphinic acid), butylene-1, 2-bis (propylphosphinic acid), butylene-1, 2-bis (butylphosphinic acid), butylene-1, 2-bis (pentylphosphinic acid), butylene-1, 2-bis (hexylphosphinic acid), hexylene-1, 2-bis (ethylphosphinic acid), hexylene-1, 2-bis (propylphosphinic acid), hexylene-1, 2-bis (butylphosphinic acid), hexylene-1, 2-bis (pentylphosphinic acid) or hexylene-1, 2-bis (hexylphosphinic acid), and the alkylphosphonic acid is ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid or hexylphosphonic acid.

Preferably, the mixture further comprises at least one synergist.

Preferably, the synergist is a nitrogen containing compound such as melem, melam, Melon (Melon), melamine borate, melamine cyanurate, melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetramelamine triphosphate, hexamelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate and/or Melon polyphosphate.

Preferably, the synergist is also an aluminium compound, a magnesium compound, a tin compound, an antimony compound, a zinc compound, a silicon compound, a phosphorus compound, a carbodiimide, a phosphazene, a piperazine (pyro) phosphate, (poly) isocyanate and/or a styrene-acrylic polymer.

In particular, the synergist is aluminium hydroxide, halloysite, sapphire products, boehmite, nano-boehmite; magnesium hydroxide; antimony oxide; tin oxide; zinc oxide, zinc hydroxide, zinc oxide hydrate, zinc carbonate, zinc stannate, zinc hydroxystannate, zinc silicate, zinc phosphate, zinc borophosphate, zinc borate and/or zinc molybdate; phosphinic acid and salts thereof, phosphonic acid and salts thereof and/or phosphine oxides; methyl biscaprolactam.

Furthermore, the synergist is preferably a nitrogen-containing compound selected from the group consisting of tris (hydroxyethyl) isocyanurate and aromatic polycarboxylic acidsOr benzoguanamine, acetoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, cyanurates, cyanurate-epoxide compounds, urea cyanurates, dicyandiamide, guanidines, guanidinium phosphates and/or guanidinium sulfates.

Preferably, the mixture comprises from 99 to 1% by weight of a mixture of at least one diphosphinic acid of the formula (I) according to at least one of claims 1 to 11 and at least one alkylphosphonic acid of the formula (II) and from 1 to 99% by weight of a synergist.

The invention also relates to a process for preparing a mixture according to at least one of claims 1 to 11, characterized in that a phosphinic acid source is reacted with an alkyne in the presence of an initiator.

Preferably, the source of phosphinic acid is ethylphosphinic acid, and the alkyne is acetylene, methylacetylene, 1-butyne, 1-hexyne, 2-hexyne, 1-octyne, 4-octyne, 1-butyn-4-ol, 2-butyn-1-ol, 3-butyn-1-ol, 5-hexyn-1-ol, 1-octyn-3-ol, 1-pentyne, phenylacetylene, trimethylsilylacetylene and/or diphenylacetylene.

Preferably, the initiator is a free radical initiator having a nitrogen-nitrogen bond or an oxygen-oxygen bond.

Particularly preferably, the free-radical initiator is 2,2' -azobis (2-amidinopropane) dihydrochloride, 2' -azobis (N, N ' -dimethyleneisobutyramidine) dihydrochloride, azobisisobutyronitrile, 4' -azobis (4-cyanovaleric acid) and/or 2,2' -azobis (2-methylbutyronitrile) or is hydrogen peroxide, ammonium persulfate, potassium persulfate, dibenzoyl peroxide, di-tert-butyl peroxide, peracetic acid, diisobutyryl peroxide, isopropylphenyl neodecanoate peroxide, tert-butyl neopentanoate peroxide, tert-amyl neopentanoate peroxide, dipropyl peroxydicarbonate, dibutyl peroxydicarbonate, dimyristyl peroxydicarbonate, dilauroyl peroxide, 1-peroxy-2-ethylhexanoate, 1,3, 3-tetramethylbutyl ester, t-amyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyisobutyrate, 1-di (t-butylperoxy) cyclohexane, t-butyl peroxybenzoate, t-butyl peroxyacetate, t-butyl peroxydiethylacetate, t-butyl peroxyisopropylcarbonate, 2-di (t-butylperoxy) butane, t-amyl hydroperoxide and/or 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.

Preferably, the solvent is a linear or branched alkane, an alkyl substituted aromatic solvent, an alcohol or ether immiscible or only partially miscible with water, water and/or acetic acid.

Preferably, the alcohol is methanol, propanol, isobutanol and/or n-butanol or a mixture of these alcohols with water.

Preferably, the reaction temperature is 50-150 ℃.

The invention also relates to the use of mixtures of at least one diphosphinic acid of the formula (I) with at least one alkylphosphonic acid of the formula (II) according to at least one of claims 1 to 11 as an intermediate for further syntheses, as binders, as crosslinkers or accelerators for curing epoxy resins, polyurethane and unsaturated polyester resins, as polymer stabilizers, as plant protection agents, as chelating agents, as mineral oil additives, as corrosion inhibitors, in detergent and cleaning agent applications and in electronic applications.

The invention furthermore relates to the use of mixtures of at least one diphosphinic acid of the formula (I) with at least one alkylphosphonic acid of the formula (II) according to at least one of claims 1 to 13 as flame retardants, in particular as flame retardants for varnishes and intumescent coatings, as flame retardants for wood and other cellulose-containing products, as reactive and/or nonreactive flame retardants for polymers, for the preparation of flame-retardant polymer molding materials, for the preparation of flame-retardant polymer moldings and/or for imparting flame retardancy to polyesters and also to pure and blended cellulose fabrics by impregnation, and as synergists.

The invention also comprises flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 0.5 to 99.5% by weight of a mixture according to at least one of claims 1 to 13, from 0.5 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 0 to 55% by weight of additives and from 0 to 55% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

Finally, the invention relates to flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 1 to 30% by weight of a mixture according to at least one of claims 1 to 13, from 10 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 2 to 30% by weight of additives and from 2 to 30% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

Preferably, R¹And R²Identical or different and denotes H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl; r³(independent of R)¹And R²) Preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butylButyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl; and R⁴Represents ethylene, butylene, hexylene or octylene; thus means C connecting two P atoms₂、C₄、C₆Or C₈A group.

Preference is also given to mixtures of from 98 to 99.9% by weight of ethylene-1, 2-bis (ethylphosphinic acid) and from 2 to 0.1% by weight of ethylphosphinic acid.

Preferred binary mixtures of at least one diphosphonic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) consist of the following:

ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid,

ethylene-1, 2-bis (ethylphosphinic acid) and propylphosphonic acid,

ethylene-1, 2-bis (ethylphosphinic acid) and butylphosphonic acid,

ethylene-1, 2-bis (ethylphosphinic acid) and pentylphosphonic acid,

ethylene-1, 2-bis (ethylphosphinic acid) and hexylphosphonic acid,

ethylene-1, 2-bis (propylphosphinic acid) and ethylphosphonic acid,

ethylene-1, 2-bis (propylphosphinic acid) and propylphosphonic acid,

ethylene-1, 2-bis (propylphosphinic acid) and butylphosphonic acid,

ethylene-1, 2-bis (propylphosphinic acid) and pentylphosphonic acid,

ethylene-1, 2-bis (propylphosphinic acid) and hexylphosphonic acid,

ethylene-1, 2-bis (butylphosphinic acid) and ethylphosphonic acid,

ethylene-1, 2-bis (butylphosphinic acid) and propylphosphonic acid,

ethylene-1, 2-bis (butylphosphinic acid) and butylphosphonic acid,

ethylene-1, 2-bis (butylphosphinic acid) and pentylphosphonic acid,

ethylene-1, 2-bis (butylphosphinic acid) and hexylphosphonic acid,

ethylene-1, 2-bis (pentylphosphinic acid) and ethylphosphonic acid,

ethylene-1, 2-bis (pentylphosphinic acid) and propylphosphonic acid,

ethylene-1, 2-bis (pentylphosphinic acid) and butylphosphonic acid,

ethylene-1, 2-bis (pentylphosphinic acid) and pentylphosphonic acid,

ethylene-1, 2-bis (pentylphosphinic acid) and hexylphosphonic acid,

ethylene-1, 2-bis (hexylphosphinic acid) and ethylphosphonic acid,

ethylene-1, 2-bis (hexylphosphinic acid) and propylphosphonic acid,

ethylene-1, 2-bis (hexylphosphinic acid) and butylphosphonic acid,

ethylene-1, 2-bis (hexylphosphinic acid) and pentylphosphonic acid,

ethylene-1, 2-bis (hexylphosphinic acid) and hexylphosphonic acid,

butylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid,

butylene-1, 2-bis (ethylphosphinic acid) and propylphosphonic acid,

butylene-1, 2-bis (ethylphosphinic acid) and butylphosphonic acid,

butylene-1, 2-bis (ethylphosphinic acid) and pentylphosphonic acid,

butylene-1, 2-bis (ethylphosphinic acid) and hexylphosphonic acid,

butylene-1, 2-bis (propylphosphinic acid) and ethylphosphonic acid,

butylene-1, 2-bis (propylphosphinic acid) and propylphosphonic acid,

butylene-1, 2-bis (propylphosphinic acid) and butylphosphonic acid,

butylene-1, 2-bis (propylphosphinic acid) and pentylphosphonic acid,

butylene-1, 2-bis (propylphosphinic acid) and hexylphosphonic acid,

butylene-1, 2-bis (butylphosphinic acid) and ethylphosphonic acid,

butylene-1, 2-bis (butylphosphinic acid) and propylphosphonic acid,

butylene-1, 2-bis (butylphosphinic acid) and butylphosphonic acid,

butylene-1, 2-bis (butylphosphinic acid) and pentylphosphonic acid,

butylene-1, 2-bis (butylphosphinic acid) and hexylphosphonic acid,

butylene-1, 2-bis (pentylphosphinic acid) and ethylphosphonic acid,

butylene-1, 2-bis (pentylphosphinic acid) and propylphosphonic acid,

butylene-1, 2-bis (pentylphosphinic acid) and butylphosphonic acid,

butylene-1, 2-bis (pentylphosphinic acid) and pentylphosphonic acid,

butylene-1, 2-bis (pentylphosphinic acid) and hexylphosphonic acid,

butylene-1, 2-bis (hexylphosphinic acid) and ethylphosphonic acid,

butylene-1, 2-bis (hexylphosphinic acid) and propylphosphonic acid,

butylene-1, 2-bis (hexylphosphinic acid) and butylphosphonic acid,

butylene-1, 2-bis (hexylphosphinic acid) and pentylphosphonic acid,

butylene-1, 2-bis (hexylphosphinic acid) and hexylphosphonic acid,

hexamethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid,

hexamethylene-1, 2-bis (ethylphosphinic acid) and propylphosphonic acid,

hexamethylene-1, 2-bis (ethylphosphinic acid) and butylphosphonic acid,

hexamethylene-1, 2-bis (ethylphosphinic acid) and pentylphosphonic acid,

hexamethylene-1, 2-bis (ethylphosphinic acid) and hexylphosphonic acid,

hexamethylene-1, 2-bis (propylphosphinic acid) and ethylphosphonic acid,

hexamethylene-1, 2-bis (propylphosphinic acid) and propylphosphonic acid,

hexamethylene-1, 2-bis (propylphosphinic acid) and butylphosphonic acid,

hexamethylene-1, 2-bis (propylphosphinic acid) and pentylphosphonic acid,

hexamethylene-1, 2-bis (propylphosphinic acid) and hexylphosphonic acid,

hexamethylene-1, 2-bis (butylphosphinic acid) and ethylphosphonic acid,

hexamethylene-1, 2-bis (butylphosphinic acid) and propylphosphonic acid,

hexamethylene-1, 2-bis (butylphosphinic acid) and butylphosphonic acid,

hexamethylene-1, 2-bis (butylphosphinic acid) and pentylphosphonic acid,

hexamethylene-1, 2-bis (butylphosphinic acid) and hexylphosphonic acid,

hexamethylene-1, 2-bis (pentylphosphinic acid) and ethylphosphonic acid,

hexamethylene-1, 2-bis (pentylphosphinic acid) and propylphosphonic acid,

hexamethylene-1, 2-bis (pentylphosphinic acid) and butylphosphonic acid,

hexamethylene-1, 2-bis (pentylphosphinic acid) and pentylphosphonic acid,

hexamethylene-1, 2-bis (pentylphosphinic acid) and hexylphosphonic acid,

hexamethylene-1, 2-bis (hexylphosphinic acid) and ethylphosphonic acid,

hexamethylene-1, 2-bis (hexylphosphinic acid) and propylphosphonic acid,

hexamethylene-1, 2-bis (hexylphosphinic acid) and butylphosphonic acid,

hexamethylene-1, 2-bis (hexylphosphinic acid) and pentylphosphonic acid,

hexamethylene-1, 2-bis (hexylphosphinic acid) and hexylphosphonic acid.

Also mixtures of plural units may be present, for example mixtures of ethylene-1, 2-bis (ethylphosphinic acid), ethylphosphinic acid and butylphosphinic acid; or for example ethylene-1, 2-bis (ethylphosphinic acid), ethylene-1, 2-bis (butylphosphinic acid), mixtures of ethylphosphinic acid and butylphosphinic acid, and the like.

Particularly preferably, R¹、R²And R³Identical or different and denotes ethyl or butyl.

Preferably, the synergist is an intumescent neutral substance, i.e. its dimensions do not change under heat or similar load. The change can be measured by means of the coefficient of thermal expansion. This describes the dimensional change of the substance as the temperature changes.

Preferably, the mixture comprises 65 to 1% by weight of a mixture of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) according to at least one of claims 1 to 11 and 1 to 35% by weight of a synergist. Preferably, the mixture also comprises 80 to 95% by weight of a mixture of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) according to at least one of claims 1 to 11 and 5 to 20% by weight of a synergist.

In the process of the present invention, a phosphinic acid source is reacted with an alkyne in the presence of an initiator. In this case, the alkene is typically first reacted with phosphinic acid to form alkylphosphinic acid and then reacted further with alkyne to form the mixture according to the invention.

In this case, the phosphinic acid itself is preferably reacted with ethylene in the presence of a (metallocene) catalyst to form ethylphosphinic acid and the latter, after purification, is reacted with acetylene in the presence of an initiator to form a mixture of diphosphinic acids of the formula (I) according to the invention and at least one alkylphosphonic acid of the formula (II).

The mixture according to the invention of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) is preferably processed by mixing into a polymer system.

The mixing is usually carried out by kneading, dispersing and/or extruding.

Preferably, the mixture according to the invention of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) is also used by means of additive incorporation into polymer systems.

It is particularly preferred to use mixtures of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) according to the invention by means of reactive incorporation into polymer systems. The reactive incorporation is characterized by a permanent bond to the polymer extrudate of the polymer system, so that the mixture according to the invention of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) cannot bleed out.

The mixtures according to the invention can be used together with other flame retardants and other synergists. The other flame retardants include, for example, phosphorus compounds such as phosphinates, phosphonates, phosphates, phosphonic acids, phosphinic acids, phosphoric acids, phosphines, phosphine oxides, phosphorus oxides, and the like.

Suitable polymer additives for flame-retardant polymer molding materials and polymer moldings are UV absorbers, light stabilizers, lubricants, colorants, antistatic agents, nucleating agents, fillers, synergists, reinforcing agents and the like.

Preferably, the polymer system is derived from a thermoplastic polymer such as polyamide, polyester or polystyrene and/or a thermosetting polymer.

Preferably, the thermosetting polymer is an epoxy resin.

Preferably, the thermosetting polymer is an epoxy resin which has been cured with phenol and/or dicyandiamide (more generally: phenol derivatives (resols); alcohols and amines, especially phenol derivatives and dicyandiamide.

Particularly preferably, the thermosetting polymer is an epoxy resin which has been cured with a phenol and/or a dicyandiamide and/or a catalyst.

Preferably, the catalyst is an imidazole compound.

Preferably, the epoxy resin is a polyepoxide.

Preferably, the epoxy resin is a novolac-and bisphenol-a-based resin. Preferably, the polymer is a polymer of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene; and polymers of cyclic olefins, such as cyclopentene or norbornene; and polyethylene (which may optionally be crosslinked), such as High Density Polyethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density ultra high molecular weight polyethylene (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), branched low density polyethylene (VLDPE) and mixtures thereof.

Preferably, the polymers are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, Linear Low Density Polyethylene (LLDPE) and mixtures thereof with Low Density Polymers (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene-acrylic acid copolymers and salts thereof (ionomers), and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and mixtures of such copolymers with one another, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinyl acetate copolymers, LLDPE/ethylene-acrylic acid copolymers, polyalkylene/carbon monoxide copolymers of alternating or random structure, and mixtures thereof with other polymers, for example polyamides.

Preferably, the polymer is a hydrocarbon resin (e.g., C)₅-C₉) Including hydrogenated modifications thereof (e.g., tackifier resins) and mixtures of polyalkylene and starch.

Preferably, the polymer is polystyrene (A), (B), (C), (143e (basf), poly-p-methylstyrene, poly-alpha-methylstyrene. Preferably, the polymer is a copolymer of styrene or alpha-methylstyrene with a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; more impact resistant blends of styrene copolymers with other polymers such as polyacrylates, diene polymers or ethylene-propylene-diene terpolymers; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

Preferably, the polymer is a graft copolymer of styrene or alpha-methylstyrene, for example styrene grafted to polybutadiene, styrene grafted to polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted to polybutadiene; styrene, acrylonitrile and methyl methacrylate to polybutadiene; styrene and maleic anhydride grafted to polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide to polybutadiene; styrene and maleimide to polybutadiene; styrene and alkyl acrylate or methacrylate grafted to polybutadiene; styrene and acrylonitrile to ethylene-propylene-diene terpolymers; styrene and acrylonitrile to polyalkyl acrylates or polyalkyl methacrylates; styrene and acrylonitrile to acrylate-butadiene copolymers; and mixtures thereof, for example the so-called ABS, MBS, ASA or AES polymers.

Preferably, the styrene polymer is a relatively coarse-celled foam, such as EPS (expanded polystyrene), e.g. styropor (basf) and/or a foam having relatively fine cells, such as XPS (extruded rigid polystyrene foam), e.g.(BASF). Preference is given to polystyrene foams, for exampleXPS、(Dow Chemical)、And

preferably, the polymers are halogen-containing polymers, such as polychloroprene, chlorine rubber, chlorinated and brominated isobutylene-isoprene copolymers (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene with chlorinated ethylene, epichlorohydrin homopolymers and epichlorohydrin copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

Preferably, the polymers are polymers derived from α, β -unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates impact-modified with butyl acrylate, polyacrylonitrile and polyacrylamides, and copolymers of the monomers with one another or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

Preferably, the polymer is a polymer derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate or polymaleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and copolymers thereof with olefins.

Preferably, the polymers are homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with diglycidyl ethers.

Preferably, the polymer is a polyacetal, such as polyoxymethylene and those polyoxymethylenes which contain comonomers such as ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

Preferably, the polymers are polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

The polymers are preferably polyurethanes and their precursors derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other.

Preferably, the polymer is a polyamide derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactamsAnd copolyamides such as nylon 2/12; nylon 4 (poly-4-aminobutyric acid,4, DuPont corporation); nylon 4/6 (poly (tetramethylene adipamide),4/6, DuPont corporation); nylon 6 (polycaprolactam, poly-6-aminocaproic acid,6, DuPont corporation; akulon K122, DSM;7301, DuPont corporation;b29, Bayer corporation); nylon 6/6 (poly-N, N' -hexamethylene adipate diamide,6/6, DuPont corporation;

101, DuPont corporation; durethan A30,AKV、AM, Bayer corporation;a3, BASF corporation); nylon 6/9 (poly (hexamethylene nonanoyl amide),6/9, DuPont corporation); nylon 6/10 (poly (hexamethylene sebacamide),6/10, DuPont corporation); nylon 6/12 (poly (hexamethylene dodecanediamide),6/12, DuPont corporation), nylon 6/66 (poly (hexamethylene adipamide-co-caprolactam),6/66, DuPont corporation); nylon 7 (poly-7-aminoheptanoic acid,7, DuPont corporation); nylon 7,7 (polyheptamethylene pimelamide,7,7, DuPont corporation); nylon 8 (poly-8-aminocaprylic acid,DuPont corporation); nylon 8,8 (poly octamethylene octanediamide,8,8, DuPont), nylon 9 (poly-9-aminononanoic acid,9, DuPont), nylon 9,9 (poly nonamethylene azelamide,9,9, DuPont), nylon 10 (poly-10-aminodecanoic acid,10, DuPont corporation), nylon 10,9 (poly (decamethylene azelamide),10,9, DuPont), nylon 10,10 (poly (decamethylene sebacamide),10,10, DuPont), nylon 11 (poly-11-aminoundecanoic acid,11, DuPont), nylon 12 (polylauryllactam,12, DuPont company;l20, Ems Chemie corporation); aromatic polyamides starting from meta-xylene, diamines and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid (polyhexamethyleneisophthalamide, polyhexamethyleneterephthalamide) and optionally elastomers as modifiers, for example poly-2, 4, 4-trimethylhexamethyleneterephthalamide or poly-m-phenyleneisophthalamide. Block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. In addition, there are polyamides or copolyamides modified with EPDM (ethylene-propylene-diene rubber) or ABS (acrylonitrile-butadiene-styrene); and polyamides condensed during processing ("RIM polyamide systems"). Preferably, the polymers are polyureas, polybenzimidazoles, polyimides, polyamideimides, polyetherimides, polyesterimides, and polyhydantoins. Preferably, the polymer is a polyester derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate: (2500、2002, Celanesse corporation;BASF corporation), poly 1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates; and block polyetheresters derived from polyethers having hydroxyl end groups; and polyesters modified with polycarbonates or MBS.

Preferably, the polymers are polycarbonates and polyester carbonates.

Preferably, the polymer is polysulfone, polyethersulfone and polyetherketone.

Preferably, the polymers are crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.

Preferably, the polymer is a drying or non-drying alkyd resin.

Preferably, the polymer is an unsaturated polyester resin derived from saturated and unsaturated dicarboxylic acids and polyols and vinyl compounds as crosslinkers and halogen-containing low flammability modifiers thereof.

Preferably, the polymer is a crosslinkable acrylic resin derived from a substituted acrylate, for example from an epoxy acrylate, a urethane or a polyester acrylate.

Preferably, the polymers are alkyd, polyester and acrylate resins, which have been crosslinked with melamine, urea, isocyanate, isocyanurate, polyisocyanate or epoxy resins.

Preferably, the polymer is a crosslinked epoxy resin derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, which are crosslinked by means of conventional curing agents such as anhydrides or amines (with or without accelerators).

Preferably, the polymer is a mixture (polymer blend) of the above-mentioned polymers, such as PP/EPDM (polypropylene/ethylene-propylene-diene rubber), polyamide/EPDM or ABS (polyamide/ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC/EVA (polyvinyl chloride/ethylene-vinyl acetate), PVC/ABS (polyvinyl chloride/acrylonitrile-butadiene-styrene), PVC/MBS (polyvinyl chloride/methacrylate-butadiene-styrene), PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene), PBTP/ABS (polybutylene terephthalate/acrylonitrile-butadiene-styrene), poly (ethylene-propylene-co-diene-styrene), poly (ethylene-co-ethylene-butylene-co-ethylene-co-butylene-styrene), poly (ethylene-propylene-diene-co-butylene-styrene), poly (ethylene-co-propylene, PC/ASA (polycarbonate/acrylate-styrene-acrylonitrile), PC/PBT (polycarbonate/polybutylene terephthalate), PVC/CPE (polyvinyl chloride/chlorinated polyethylene), PVC/acrylate (polyvinyl chloride/acrylate), POM/thermoplastic PUR (polyoxymethylene/thermoplastic polyurethane), PC/thermoplastic PUR (polycarbonate/thermoplastic polyurethane), POM/acrylate (polyoxymethylene/acrylate), POM/MBS (polyoxymethylene/methacrylate-butadiene-styrene), PPO/HIPS (polyphenylene oxide/high impact polystyrene), PPO/PA6,6 (polyphenylene oxide/nylon 6,6) and copolymers, PA/HDPE (polyamide/high density polyethylene), PA/PP (polyamide/polyethylene), PA/PPO (polyamide/polyphenylene oxide), PBT/PC/ABS (polybutylene terephthalate/polycarbonate/acrylonitrile-butadiene-styrene) and/or PBT/PET/PC (polybutylene terephthalate/polyethylene terephthalate/polycarbonate).

The polymer may be laser markable.

Preferably, the prepared molded article is in a rectangular shape having a regular or irregular bottom surface, or in a cubic shape, a rectangular shape, a mat shape or a prismatic shape.

The invention is illustrated by the following examples.

Production, processing and testing of flame-retardant polymer molding materials and flame-retardant polymer moldings

Mixing a flame retardant component with the polymer particlesThe materials and possible additives are mixed and introduced into a twin-screw extruder (type: Leistritz) having a temperature of 230 ℃ to 260 ℃ (PBT-GV) or 260 ℃ to 280 ℃ (PA66-GV)30/34) is provided. The homogenized polymer strand is drawn off, cooled in a water bath and then granulated.

After sufficient drying, the molding materials were processed on an injection molding machine (model: AarburgAllrounder) at a material temperature of 240 ℃ to 270 ℃ (PBT-GV) or 260 ℃ to 290 ℃ (PA66-GV) to give test specimens. The test specimens were tested for flame retardancy (fire resistance) and rated by means of the UL 94 test (Underwriter Laboratories).

The UL 94 fire rating (Underwriter Laboratories) is determined on a 1.5mm thick test specimen for the test specimens consisting of the respective mixtures.

The following fire ratings were obtained according to UL 94:

v-0: the ignition time is not more than 10 seconds, the total ignition time of 10 times of ignition is not more than 50 seconds, no combustion drips, the sample is not completely combusted, and no residual glow of the sample is generated within more than 30 seconds after the ignition is finished;

v-1: the ignition time after the ignition is finished does not exceed 30 seconds, the total ignition time after 10 times of ignition does not exceed 250 seconds, no sample residue is generated after more than 60 seconds after the ignition is finished, and other standards are the same as those of V-0;

v-2: igniting cotton wool by burning and dripping, and the other standards are the same as those of V-1;

non-gradeable (nkl): does not satisfy the fire-fighting class V-2.

In addition, some of the samples tested were subjected to LOI value measurement. The LOI value (limiting oxygen index) is determined according to ISO 4589. According to ISO4589, LOI corresponds to the volume percentage of the lowest oxygen concentration in a mixture of oxygen and nitrogen that is just capable of maintaining the combustion of plastics. The higher the LOI value, the more difficult the material tested is to burn.

LOI23 combustible

LOI24-28 conditional combustible

LOI29-35 flame retardant

LOI >36 is particularly flame retardant

Chemicals and abbreviations used:

novolac resin:PF 0790, Hexion Corp

Initiator:67, DuPont Corp

In principle, the process according to the invention is carried out in such a way that the reaction mixture is subjected to a relatively low acetylene flow rate of only a maximum of 1l/h under the given reaction conditions. After the acetylene is conducted through the reaction solution until sufficient conversion and for a sufficient continuous reaction time, the acetylene feed is stopped and worked up under oxygen or air. For this purpose, for example, the reaction mixture is blown off with oxygen, the acetylene is driven off from the apparatus with oxygen, and the product mixture is worked up.

All amounts are weight% unless otherwise indicated.

Example 1

5852g of tetrahydrofuran are placed in a three-necked flask with stirrer and high-performance condenser at room temperature and "degassed" with stirring and introduction of nitrogen, and all further reactions are carried out under nitrogen. 70mg of tris (dibenzylideneacetone) dipalladium and 95mg of 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene were then added and stirred for a further 15 minutes. 198g of phosphinic acid in 198g of water are added with stirring. The reaction solution was transferred to a 2L B uchi reactor. While stirring the reaction mixture, the reactor was charged with 2.5 bar of ethylene and the reaction mixture was heated to 80 ℃. After 56g of ethylene had been taken up, it was cooled to room temperature and burnt to remove free ethylene.

The reaction mixture is freed of solvent on a rotary evaporator at up to 60 ℃ and 350-10 mbar. To the residue was added 300g of completely desalted water, and stirred at room temperature for 1 hour under a nitrogen atmosphere. The resulting residue was filtered, and the filtrate was extracted with 200ml of toluene. The aqueous phase is freed of solvent on a rotary evaporator at up to 60 ℃ and 250-10 mbar.

³¹P NMR(D₂O, coupling): double peak in multiplet, 36.7 ppm.

Example 2

0.5mol of ethylphosphinic acid from example 1 are prepended in butanol and inertized and heated to 80 ℃ with stirring. Acetylene is introduced into the reaction solution, 0.4 mol% of initiator is metered in over 3 hours, and the reaction is continued. The acetylene feed was stopped and the acetylene was purged from the apparatus with nitrogen. After cooling the reaction mixture, the solid formed is filtered off with suction and redispersed with acetone, washed and dried in a vacuum oven at 100 ℃ for 4 hours.

33.2g of a mixture of ethylene-1, 2-bis (ethylphosphinic acid) (99.9% by weight) and ethylphosphonic acid (0.1% by weight) were obtained in a yield of 62%.

Example 3

0.5mol of ethylphosphinic acid from example 1 are prepended in butanol and inertized and heated to 80 ℃ with stirring. Acetylene is introduced into the reaction solution and 0.4 mol% of initiator is metered in over 2.5 hours and the reaction is continued. The acetylene feed was stopped and the acetylene was purged from the apparatus with nitrogen. After cooling the reaction mixture, the solid formed is filtered off with suction and redispersed with acetone, washed and dried in a vacuum oven at 100 ℃ for 4 hours.

36.3g of a mixture of ethylene-1, 2-bis (ethylphosphinic acid) (98% by weight) and ethylphosphinic acid (2% by weight) were obtained in a yield of 68%.

Example 4

0.5mol of ethylphosphinic acid from example 1 are prepended in butanol and inertized with stirring and heated to 90 ℃. Acetylene is introduced into the reaction solution and 0.5 mol% of initiator is metered in over 2 hours and the reaction is continued. The acetylene feed was stopped and the acetylene was purged from the apparatus with nitrogen. After cooling the reaction mixture, the solid formed is filtered off with suction and redispersed with acetone, washed and dried in a vacuum oven at 100 ℃ for 4 hours.

33.8g of a mixture of ethylene-1, 2-bis (ethylphosphinic acid) (90% by weight) and ethylphosphinic acid (10% by weight) were obtained in a yield of 63%.

Example 5

0.5mol of ethylphosphinic acid from example 1 are prepended in butanol and inertized with stirring and heated to 100 ℃. Acetylene is introduced into the reaction solution, 0.8 mol% of initiator is metered in over 2 hours, and the reaction is continued. The acetylene feed was stopped and the acetylene was purged from the apparatus with nitrogen. After cooling the reaction mixture, the solid formed is filtered off with suction, redispersed with acetone, washed and dried in a vacuum oven at 100 ℃ for 4 hours.

40.6g of a mixture of ethylene-1, 2-bis (ethylphosphinic acid) (60% by weight) and ethylphosphinic acid (40% by weight) were obtained in a yield of 75%.

Example 6

0.5mol of ethylphosphinic acid from example 1 are prepended in butanol and inertized with stirring and heated to 100 ℃. Acetylene is introduced into the reaction solution, 1.0 mol% of initiator is metered in over 2 hours, and the reaction is continued. The acetylene feed was stopped and the acetylene was purged from the apparatus with nitrogen. After cooling the reaction mixture, the solid formed is filtered off with suction, redispersed with acetone, washed and dried in a vacuum oven at 100 ℃ for 4 hours.

38.5g of a mixture of ethylene-1, 2-bis (ethylphosphinic acid) (50% by weight) and ethylphosphinic acid (50% by weight) were obtained in a yield of 71%.

General procedure for preparing Polymer moldings

a) Preparation of phosphorus-modified epoxy resins

1000g of epoxy resin (e.g., Beckopox EP140) was placed in a 2L five-necked flask setup. It was heated to 110 ℃ over 1 hour and the volatile components were removed in vacuo.

The reaction mixture was then inertized with nitrogen and the temperature in the flask was raised to 170 ℃. In each case 118g of a mixture of phosphorus compounds (selected from examples 2 to 6) were added under stirring and flowing nitrogen, an exothermic reaction being observed here. The resulting resin was yellow in color and flowable.

b) Preparation of epoxy resin samples

100 parts of phosphorus-modified epoxy resin are mixed with a novolak resin having an equivalent OH equivalent (hydroxide equivalent 105g/mol, melting point 85-95 ℃) and heated to 150 ℃. Where the components are liquefied. Stir slowly until a homogeneous mixture is produced and cool to 130 ℃. At this point 0.03 parts of 2-phenylimidazole is added and stirred for a further 5-10 minutes. Subsequently, the deposit was poured hot into a dish and cured at 140 ℃ for 2 hours and at 200 ℃ for 2 hours.

c) Preparation of epoxy resin laminate

In 63 parts of acetone and 27 parts ofTo the PM, 100 parts of a phosphorus-modified epoxy resin according to b) are added, and the corresponding amount of phenolic resin is added. The precipitate was stirred for 30 minutes at which time 2-phenylimidazole was added. Subsequently, the deposit was filtered through a 400 μm sieve to removeExcess resin particles. At this time, the glass fabric (7628 type, 203 g/m)²) Immersed in the solution until the fabric is completely wetted. The wetted fabric was pulled from the mixture and excess resin was removed. Subsequently, the wetted fabric is precured in stages in a drying oven at a temperature of at most 165 ℃ for a short time and then cured in a hot press. The cured laminate has a resin content of 30 to 50 wt.%. The thermal expansion of the molded article (laminate) obtained was measured according to ASTM E831-06.

Example 7

According to the step of preparing the polymer-molded article, a laminate was prepared using 100% by weight of bisphenol A resin. Having the values of the coefficients of thermal expansion given in the table.

Example 8

Pure ethylene-1, 2-bis (ethylphosphinic acid) was obtained by washing the product mixture from example 2 with acetone several times until ethylphosphonic acid could no longer be detected.

According to the general procedure for preparing polymer moldings, a composition of 90% of a bisphenol A resin with a curing agent and a catalyst and 10% of ethylene-1, 2-bis (ethylphosphinic acid) was used to prepare moldings.

Example 9

According to EP-A-2178891, ethylphosphinic acid is obtained from phosphinic acid by means of ｃA catalyst and ethylene, and purified by means of esterification and distillation. Pure ethylphosphonic acid is obtained by subsequent oxidation with oxygen.

According to the general procedure for the preparation of polymer moldings, a composition of 90% of bisphenol A resin with curing agent and catalyst and 10% of the obtained ethylphosphonic acid was used to prepare moldings.

Example 10

According to the general procedure for the preparation of polymer moldings, moldings were prepared using a mixture according to the invention of 90% of bisphenol A resin with curing agent and catalyst and 10% of ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid from example 2.

Example 11

According to the general procedure for the preparation of polymer moldings, moldings were prepared using a mixture according to the invention of 90% of bisphenol A resin with curing agent and catalyst and 10% of ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid from example 3.

Example 12

According to the general procedure for the preparation of polymer moldings, moldings were prepared using a mixture according to the invention of 90% of bisphenol A resin with curing agent and catalyst and 10% of ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid from example 4.

Example 13

According to the general procedure for preparing polymer moldings, moldings are prepared using a mixture according to the invention of 90% of bisphenol A resin with curing agent and catalyst and 10% of ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid from example 5.

Example 14

According to the general procedure for preparing polymer moldings, moldings are prepared using a mixture according to the invention of 90% of bisphenol A resin with curing agent and catalyst and 10% of ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid from example 6.

The results are reproduced in the following table:

the mixtures from examples 5 and 6 likewise lead to a reduction in the coefficient of thermal expansion.

The coefficient of thermal expansion of the laminates of the substance mixtures according to the invention with ethylene-1, 2-bis (ethylphosphinic acid) and ethylphosphonic acid is reduced compared with the pure laminates (example 7); and therefore the thermal expansion is extremely low. An increase in the proportion of ethylphosphonic acid leads to a further improvement. The products according to the invention result in moldings which are produced having a lower expansion and therefore meet the requirements for dimensional stability.

Example 15: production of polyester-based polymer moldings

a) Preparation of phosphorus-modified polyethylene terephthalate

1000g of dimethyl terephthalate were mixed with 720ml of ethylene glycol and 230mgMn (OCOCH)₃)₄·4H₂The O was transesterified at a temperature of 170-220 ℃ under a nitrogen atmosphere. After separation of the methanol, 17.2g of the mixture according to the invention from example 4 were added thereto at 220 ℃ and 350mg of Sb were added₂O₃Thereafter, the autoclave was again warmed to 250 ℃ while applying vacuum. Polymerization was carried out at 0.2mm Hg and 287 ℃ for 2 hours. The resulting product had a melting point of 240 ℃ and 244 ℃ and a phosphorus content of 0.5% and was present as pellets.

b) Production of Plastic molded articles

The polymer pellets thus obtained were mixed with possible additives and introduced into a twin-screw extruder (model: Leistritz LSM30/34) having a temperature of 250-290 ℃ (PET-GV). The homogenized polymer strand was drawn off, cooled in a water bath and then granulated.

After sufficient drying, the molding materials were processed on an injection molding machine (model: AarburgAllrounder) at a material temperature of 250 ℃ and 300 ℃ (PET-GV) to give test specimens.

A specimen having a thickness of 1.6mm was measured for UL 94 fire rating and LOI.

A molded article having a thickness of 1.6mm gave V-0 and an LOI of 28%.

Claims (24)

1. A mixture of at least one diphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II),

R¹，R²representation H, C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl radical, C₇-C₁₈An alkylaryl group;

R⁴is represented by C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl radical, C₇-C₁₈An alkylaryl group;

wherein:

R³representation H, C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl and/or C₇-C₁₈An alkylaryl group.

2. The mixture according to claim 1, wherein R is¹、R²And R³Identical or different and denotes H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl, and R⁴Represents ethylene, butylene, hexylene or octylene.

3. Mixture according to claim 1 or 2, characterized in that it comprises 0.1 to 99.9% by weight of diphosphinic acids of the formula (I) and 99.9 to 0.1% by weight of alkylphosphonic acids of the formula (II).

4. The mixture according to any one or more of claims 1 to 3, characterized in that it comprises from 40 to 99.9% by weight of diphosphinic acids of the formula (I) and from 60 to 0.1% by weight of alkylphosphonic acids of the formula (II).

5. Mixture according to one or more of claims 1 to 4, characterized in that it comprises 60 to 99.9% by weight of diphosphinic acids of the formula (I) and 40 to 0.1% by weight of alkylphosphonic acids of the formula (II).

6. The mixture according to any one or more of claims 1 to 5, characterized in that it comprises from 80 to 99.9% by weight of diphosphinic acids of the formula (I) and from 20 to 0.1% by weight of alkylphosphonic acids of the formula (II).

7. The mixture according to any one or more of claims 1 to 6, characterized in that it comprises 90 to 99.9% by weight of diphosphinic acids of the formula (I) and 10 to 0.1% by weight of alkylphosphonic acids of the formula (II).

8. Mixture according to one or more of claims 1 to 7, characterized in that it comprises 95 to 99.9% by weight of diphosphinic acids of the formula (I) and 5 to 0.1% by weight of alkylphosphonic acids of the formula (II).

9. Mixture according to one or more of claims 1 to 8, characterized in that it comprises 98 to 99.9% by weight of diphosphinic acids of the formula (I) and 2 to 0.1% by weight of alkylphosphonic acids of the formula (II).

10. Mixture according to one or more of claims 1 to 9, characterised in that the diphosphinic acid is ethylene-1, 2-bis (ethylphosphinic acid), ethylene-1, 2-bis (propylphosphinic acid), ethylene-1, 2-bis (butylphosphinic acid), ethylene-1, 2-bis (pentylphosphinic acid), ethylene-1, 2-bis (hexylphosphinic acid), butylene-1, 2-bis (ethylphosphinic acid), butylene-1, 2-bis (propylphosphinic acid), butylene-1, 2-bis (butylphosphinic acid), butylene-1, 2-bis (pentylphosphinic acid), butylene-1, 2-bis (hexylphosphinic acid), hexylene-1, 2-bis (ethylphosphinic acid), Hexamethylene-1, 2-bis (propylphosphinic acid), hexamethylene-1, 2-bis (butylphosphinic acid), hexamethylene-1, 2-bis (pentylphosphinic acid) or hexamethylene-1, 2-bis (hexylphosphinic acid); and the alkyl phosphonic acid is ethyl phosphonic acid, propyl phosphonic acid, butyl phosphonic acid, pentyl phosphonic acid, or hexyl phosphonic acid.

11. Mixture according to one or more of claims 1 to 10, characterized in that it comprises 98 to 99.9% by weight of ethylene-1, 2-bis (ethylphosphinic acid) and 2 to 0.1% by weight of ethylphosphonic acid.

12. Mixture according to one or more of claims 1 to 11, characterized in that it further comprises at least one synergist which is a nitrogen-containing compound such as melem, melam, melon, melamine borate, melamine cyanurate, melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetramelamine triphosphate, hexamelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate and/or melon polyphosphate;

aluminum compounds such as aluminum hydroxide, halloysite, sapphire products, boehmite, nano-boehmite;

magnesium compounds such as magnesium hydroxide;

tin compounds such as tin oxide;

antimony compounds such as antimony oxide;

zinc compounds such as zinc oxide, zinc hydroxide, zinc oxide hydrate, zinc carbonate, zinc stannate, zinc hydroxystannate, zinc silicate, zinc phosphate, zinc borophosphate, zinc borate and/or zinc molybdate;

silicon compounds such as silicates and/or silicones;

phosphorus compounds such as phosphinic acid and salts thereof, phosphonic acid and salts thereof and/or phosphine oxides, phosphazene and/or piperazine (pyro) phosphate;

carbodiimide, piperazine, (poly) isocyanate, styrene-acrylic polymer and/or methyl biscaprolactam;

a nitrogen-containing compound selected from the group consisting of an oligoester of tris (hydroxyethyl) isocyanurate and an aromatic polycarboxylic acid, or benzoguanamine, acetoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, cyanurate-epoxide compound, urea cyanurate, dicyandiamide, guanidine phosphate and/or guanidine sulfate.

13. Mixture according to one or more of claims 1 to 12, characterized in that it comprises 99 to 1% by weight of a mixture of at least one diphosphinic acid of the formula (I) according to at least one of claims 1 to 11 and at least one alkylphosphonic acid of the formula (II) and 1 to 99% by weight of a synergist.

14. Process for the preparation of a mixture according to at least one of claims 1 to 11, characterized in that a phosphinic acid source is reacted with an alkyne in a solvent in the presence of an initiator.

15. The process according to claim 14, characterized in that the source of phosphinic acid is ethylphosphinic acid and the alkyne is acetylene, methylacetylene, 1-butyne, 1-hexyne, 2-hexyne, 1-octyne, 4-octyne, 1-butyn-4-ol, 2-butyn-1-ol, 3-butyn-1-ol, 5-hexyn-1-ol, 1-octyn-3-ol, 1-pentyne, phenylacetylene, trimethylsilylacetylene and/or diphenylacetylene.

16. The process according to claim 14 or 15, characterized in that the initiator is a radical initiator having a nitrogen-nitrogen bond or an oxygen-oxygen bond.

17. The process according to claim 16, characterized in that the free radical initiator is 2,2' -azobis (2-amidinopropane) dihydrochloride, 2' -azobis (N, N ' -dimethyleneisobutyramidine) dihydrochloride, azobisisobutyronitrile, 4' -azobis (4-cyanovaleric acid) and/or 2,2' -azobis (2-methylbutyronitrile) or hydrogen peroxide, ammonium persulfate, potassium persulfate, dibenzoyl peroxide, di-tert-butyl peroxide, peracetic acid, diisobutyryl peroxide, isopropylphenyl neodecanoate peroxide, tert-butyl neopentanoate peroxide, tert-amyl neopentanoate peroxide, dipropyl peroxide, dibutyl peroxide, dimyristyl peroxydicarbonate, dilauroyl peroxide, lauroyl peroxide, 1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxyisobutyrate, 1-di (tert-butylperoxy) cyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisopropylcarbonate, 2-di (tert-butylperoxy) butane, tert-amyl hydroperoxide and/or 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.

18. The process according to any one or more of claims 14 to 17, characterized in that the solvent is a linear or branched alkane, an alkyl substituted aromatic solvent, a water immiscible or only partially miscible alcohol or ether, water and/or acetic acid.

19. The process according to claim 18, characterized in that the alcohol is methanol, propanol, isobutanol and/or n-butanol or a mixture of these alcohols with water.

20. The process according to one or more of claims 14 to 19, characterized in that the reaction temperature is 50 to 150 ℃.

21. Use of the mixtures according to at least one of claims 1 to 11 as intermediates for further syntheses, as binders, as crosslinkers or accelerators for curing epoxy resins, polyurethane and unsaturated polyester resins, as polymer stabilizers, as plant protection agents, as chelating agents, as mineral oil additives, as corrosion inhibitors, in detergent and cleaning agent applications and in electronic applications.

22. Use of the mixtures according to at least one of claims 1 to 13 as flame retardants, in particular as flame retardants for varnishes and intumescent coatings, as flame retardants for wood and other cellulose-containing products, as reactive and/or nonreactive flame retardants for polymers, for the preparation of flame-retardant polymer molding materials, for the preparation of flame-retardant polymer moldings and/or for imparting flame retardancy to polyesters and also pure and blended cellulose fabrics by impregnation, and/or as synergists.

23. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 0.5 to 99.5% by weight of a mixture according to at least one of claims 1 to 13, from 0.5 to 99.5% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 0 to 55% by weight of additives and from 0 to 55% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

24. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 1 to 30% by weight of a mixture according to at least one of claims 1 to 13, from 10 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 2 to 30% by weight of additives and from 2 to 30% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.