HK1198037B - Mixtures of dialkylphosphinic acids and alkylphosphonic acids, a process for preparation thereof and the use thereof - Google Patents

Description

Mixture of dialkylphosphinic acids and alkylphosphonic acids, method for the production thereof and use thereof

The invention relates to mixtures of at least one dialkylphosphinic 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).

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

The object is therefore achieved by mixtures of at least one dialkylphosphinic acid of the formula (I) with at least one alkylphosphonic acid of the formula (II),

wherein

R¹，R²Identical or different and independently of one another represent C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl radical, C₇-C₁₈An alkylaryl group;

wherein

R³Is represented by C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl and/or C₇-C₁₈An alkylaryl group.

Preferably, R¹And R²Identical or different and denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl; r³Denotes (independently of R)¹And R²) Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl.

Preferably, the mixture comprises from 0.1 to 99.9% by weight of dialkylphosphinic 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 dialkylphosphinic acids of the formula (I) and from 60 to 0.1% by weight of alkylphosphonic acids of the formula (II).

In particular, the mixture comprises from 60 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and from 40 to 0.1% by weight of alkylphosphonic acids of the formula (II).

Preferably, the mixture comprises 80 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 20 to 0.1% by weight of alkylphosphonic acids of the formula (II).

Also preferably, the mixture comprises 90 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 10 to 0.1% by weight of alkylphosphonic acids of the formula (II).

Particularly preferably, the mixture comprises 95 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 5 to 0.1% by weight of alkylphosphonic acids of the formula (II).

Particularly advantageously, the mixture comprises 98 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 2 to 0.1% by weight of alkylphosphonic acids of the formula (II).

Preferably the dialkylphosphinic acid is diethylphosphinic acid, ethylpropylphosphinic acid, ethylbutylphosphinic acid, ethylpentylphosphinic acid, ethylhexylphosphinic acid, dipropylphosphinic acid, propylbutylphosphinic acid, propylpentylphosphinic acid, propylhexylphosphinic acid, dibutylphosphinic acid, butylpentylphosphinic acid, butylhexylphosphinic acid, dipentylphosphinic acid, pentylhexylphosphinic acid and/or dihexylphosphinic acid; and the alkyl phosphonic acid is ethyl phosphonic acid, propyl phosphonic acid, butyl phosphonic acid, pentyl phosphonic acid, or hexyl phosphonic acid.

Particularly preferred is a mixture comprising 98 to 99.9% by weight of diethylphosphinic acid and 0.1 to 2% by weight of ethylphosphonic acid.

Preferably, the mixture further comprises at least one synergist.

Preferably, the synergist is 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; are aluminum compounds, magnesium compounds, tin compounds, antimony compounds, zinc compounds, silicon compounds, phosphorus compounds, carbodiimides, phosphazenes, piperazines, piperazine (pyro) phosphates, (poly) isocyanates and/or styrene-acrylic polymers.

Preferably, the synergist is also 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(ii) a Phosphinic acid and salts thereof, phosphonic acid and salts thereof and/or phosphine oxides; methyl biscaprolactam; is a nitrogen-containing compound selected from tris (hydroxyethyl) isocyanurate and aromatic polycarboxylic acidOr 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 99 to 1% by weight of a mixture of dialkylphosphinic acids of the formula (I) according to at least one of claims 1 to 11 and alkylphosphonic acids of the formula (II) and 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 phosphorus source is reacted with an olefin and a free-radical initiator and, after addition of a mineral acid and treatment, converted into a mixture of dialkylphosphinic acids according to formula (I) and alkylphosphonic acids of formula (II).

Preferably, the phosphorus source is sodium hypophosphite, the olefin is ethylene and the mineral acid is sulfuric acid.

Preferably, a solution of sodium hypophosphite is reacted with ethylene to form the salt of diethylphosphinic acid, which is then reacted with sulfuric, nitric, hydrochloric and/or acetic acid and subsequently concentrated, filtered and distilled to form a mixture of diethylphosphinic and ethylphosphonic acids.

Preferably, the reaction temperature is between 50 and 150 ℃.

The invention also relates to the 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 sequestering agents, as mineral oil additives, as corrosion inhibitors, in washing and cleaning agent applications and in electronic applications.

The invention furthermore relates to the use of mixtures of at least one dialkylphosphinic acid of the formula (I) and 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 producing flame-retardant polymer molding materials, for producing 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 45% by weight of a mixture according to at least one of claims 1 to 13, from 55 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.

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

diethyl phosphinic acid and ethyl phosphonic acid,

diethyl phosphinic acid and propyl phosphonic acid,

diethyl phosphinic acid and butyl phosphonic acid,

diethyl phosphinic acid and amyl phosphonic acid,

diethyl phosphinic acid and hexyl phosphonic acid,

ethyl propyl phosphinic acid and ethyl phosphonic acid,

ethyl propyl phosphinic acid and propyl phosphonic acid,

ethyl propyl phosphinic acid and butyl phosphonic acid,

ethyl propyl phosphinic acid and amyl phosphonic acid,

ethyl propyl phosphinic acid and hexyl phosphonic acid,

ethyl butyl phosphinic acid and ethyl phosphonic acid,

ethyl butyl phosphinic acid and propyl phosphonic acid,

ethyl butyl phosphinic acid and butyl phosphonic acid,

ethyl butyl phosphinic acid and amyl phosphonic acid,

ethyl butyl phosphinic acid and hexyl phosphonic acid,

ethyl-pentyl phosphinic acid and ethyl phosphonic acid,

ethyl-pentyl phosphinic acid and propyl phosphonic acid,

ethyl-pentyl phosphinic acid and butyl phosphonic acid,

ethyl-pentyl phosphinic acid and pentyl phosphonic acid,

ethyl-pentyl phosphinic acid and hexyl phosphonic acid,

ethyl-hexyl phosphinic acid and ethyl phosphonic acid,

ethyl-hexyl phosphinic acid and propyl phosphonic acid,

ethyl-hexyl phosphinic acid and butyl phosphonic acid,

ethyl-hexyl phosphinic acid and amyl phosphonic acid,

ethyl-hexyl phosphinic acid and hexyl phosphonic acid,

dipropylphosphinic acid and ethylphosphonic acid,

dipropylphosphinic acid and propylphosphonic acid,

dipropylphosphinic acid and butylphosphonic acid,

dipropylphosphinic acid and pentylphosphonic acid,

dipropylphosphinic acid and hexylphosphonic acid,

propylbutylphosphinic acid and ethylphosphonic acid,

propylbutylphosphinic acid and propylphosphonic acid,

propylbutylphosphinic acid and butylphosphonic acid,

propylbutylphosphinic acid and pentylphosphonic acid,

propylbutylphosphinic acid and hexylphosphonic acid,

propyl-pentyl-phosphinic acid and ethyl-phosphonic acid,

propylpentylphosphinic acid and propylphosphonic acid,

propyl-pentyl-phosphinic acid and butyl-phosphonic acid,

propyl-pentyl-phosphinic acid and pentyl-phosphonic acid,

propylpentylphosphinic acid and hexylphosphonic acid,

propylhexylphosphinic acid and ethylphosphonic acid,

propylhexylphosphinic acid and propylphosphonic acid,

propylhexylphosphinic acid and butylphosphonic acid,

propylhexylphosphinic acid and pentylphosphonic acid,

propylhexylphosphinic acid and hexylphosphonic acid,

dibutylphosphinic acid and ethylphosphonic acid,

dibutylphosphinic acid and propylphosphonic acid,

dibutylphosphinic acid and butylphosphonic acid,

dibutylphosphinic acid and pentylphosphonic acid,

dibutylphosphinic acid and hexylphosphonic acid,

butyl-pentyl-phosphinic acid and ethyl-phosphonic acid,

butyl-pentyl-phosphinic acid and propyl-phosphonic acid,

butyl-pentyl-phosphinic acid and butyl-phosphonic acid,

butyl-pentylphosphinic acid and pentylphosphonic acid,

butyl-pentyl-phosphinic acid and hexyl-phosphonic acid,

butyl hexyl phosphinic acid and ethyl phosphonic acid,

butyl hexyl phosphinic acid and propyl phosphonic acid,

butyl hexyl phosphinic acid and butyl phosphonic acid,

butyl hexyl phosphinic acid and amyl phosphonic acid,

butyl hexyl phosphinic acid and hexyl phosphonic acid,

diamyl phosphinic acid and ethyl phosphonic acid,

diamyl phosphinic acid and propyl phosphonic acid,

diamyl phosphinic acid and butyl phosphonic acid,

dipentylphosphinic acid and pentylphosphonic acid,

diamylphosphinic acid and hexylphosphonic acid,

pentylhexylphosphinic acid and ethylphosphonic acid,

pentylhexylphosphinic acid and propylphosphonic acid,

pentylhexylphosphinic acid and butylphosphonic acid,

pentylhexylphosphinic acid and pentylphosphonic acid,

pentylhexylphosphinic acid and hexylphosphonic acid,

di-hexylphosphinic acid and ethylphosphonic acid,

di-hexylphosphinic acid and propylphosphonic acid,

di-hexylphosphinic acid and butylphosphonic acid,

dihexylphosphinic acid and pentylphosphonic acid,

dihexylphosphinic acid and hexylphosphonic acid.

Also possible are ternary mixtures, such as diethylphosphinic acid and ethylphosphonic acid and butylphosphonic acid, diethylphosphinic acid and butylethylphosphinic acid and butylphosphonic acid, or quaternary mixtures, such as diethylphosphinic acid and octylphosphonic acid and butylethylphosphinic acid and ethylphosphonic acid; and other multi-component mixtures.

Particularly preferably, R¹And R²Are identical or different and represent ethyl and/or butyl, and R³Represents an ethyl or butyl group.

The invention comprises in particular a mixture of from 98 to 99.9% by weight of diethylphosphinic acid and from 2 to 0.1% by weight of ethylphosphonic acid.

Preferably, the synergist is at least one swelling neutral substance. The swelling neutral prevents or reduces polymer swelling to very low values.

Preferably, the mixture with one or more synergists comprises from 50 to 99% by weight of a mixture of at least one dialkylphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) and from 1 to 50% by weight of a synergist.

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

Particularly preferably, mixtures of at least one dialkylphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) are used 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 dialkylphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) cannot bleed out of the polymer.

The mixtures according to the invention of at least one dialkylphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) can be used with further flame retardants and further 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.

Particularly preferably, the thermosetting polymer is an epoxy resin.

Particularly 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 derived from the resins of novolac and bisphenol a.

The polymers which can be used according to the invention are thermosetting and thermoplastic polymers.

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, and 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 (α -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 example(DowChemical)、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 polymers are polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, 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 (polyThe lauryl lactam is a mixture of a lauryl lactam,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, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

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 derivatizingBlock polyetheresters 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.

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

The flame-retardant component is mixed with the polymer pellets and possible additives and introduced into a twin-screw extruder (type No.: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: Aarburg Allrounder) 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 UL94 test (Underwriter Laboratories).

The samples consisting of the respective mixtures were tested on a 1.5mm thick sample for UL94 fire rating (underwriter laboratories).

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 ignitions is not more than 50 seconds, no combustion drips, the sample is not completely burnt out, and no residual incandescence of the sample is generated more than 30 seconds after the ignition is finished.

V-1: the ignition time after the ignition is finished is not more than 30 seconds, the total ignition time after 10 times of ignition is not more than 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: the cotton wool is ignited by burning and dropping, and 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.

Chemicals and abbreviations used:

novolac resin:PF0790, Hexion Corp

The invention is illustrated by the following examples:

example 1

The sodium salt of diethylphosphinic acid was first prepared according to example 2 of EP-B-1544205, in which 1500g of sodium hypophosphite monohydrate were dissolved in 7.5kg of water and after heating the reaction mixture to 100 ℃ ethylene was introduced into the reactor until saturation. A solution of 17g of sodium persulfate in 300g of water was then metered in under ethylene pressure. The aqueous reaction solution of the sodium salt of diethylphosphinic acid obtained was converted by treatment with nitric acid, concentration, filtration and distillation (1mbar, 184 ℃) into a mixture of diethylphosphinic acid (99.9% by weight) and ethylphosphonic acid (0.1% by weight) (yield: 92%).

Example 2

An aqueous reaction solution of the sodium salt of diethylphosphinic acid was first prepared as in example 1. It was subsequently converted into a mixture of diethylphosphinic acid (98% by weight) and ethylphosphonic acid (2% by weight) (yield: 92%) by treatment with nitric acid, concentration, filtration and distillation (1mbar, 180-.

Example 3

An aqueous reaction solution of the sodium salt of diethylphosphinic acid was first prepared as in example 1, however only 95% of the desired ethylene amount was used. The solution was subsequently converted into a mixture of diethylphosphinic acid (90% by weight) and ethylphosphonic acid (10% by weight) (yield: 89%) by treatment with nitric acid, concentration, filtration and distillation (1mbar, 180-.

Example 4

An aqueous reaction solution of the sodium salt of diethylphosphinic acid was first prepared as in example 1, however only 80% of the desired ethylene amount was used. The solution was subsequently converted into a mixture of diethylphosphinic acid (60% by weight) and ethylphosphonic acid (40% by weight) (yield: 93%) by treatment with nitric acid, concentration, filtration and distillation (1mbar, 175-.

Example 5

An aqueous reaction solution of the sodium salt of diethylphosphinic acid was first prepared as in example 1, however only 75% of the desired ethylene amount was used. The solution was subsequently converted into a mixture of diethylphosphinic acid (50% by weight) and ethylphosphonic acid (50% by weight) (yield: 92%) by treatment with nitric acid, concentration, filtration and distillation (1mbar, 175-.

Step of preparing Polymer molded article

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 1 to 5) 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 remove excess 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 6

Laminates were prepared according to the general procedure for preparing polymer molded articles using 100% bisphenol a resin without portions of the mixture of diethylphosphinic acid and ethylphosphonic acid according to the present invention.

Example 7

1500g of sodium hypophosphite monohydrate were dissolved in 7.5kg of water according to example 3 of EP-B-1544205 and after heating the reaction mixture to 100 ℃ ethylene was introduced into the reactor until saturation. A solution of 32g of ammonium persulfate in 300g of water was then metered in under ethylene pressure. The product obtained is then neutralized with an equal amount of sulfuric acid and converted into diethylphosphinic acid and purified accordingly.

The molded articles were prepared according to the general procedure for preparing polymer molded articles using a composition of 90% by weight of bisphenol a resin with curing agent and catalyst and 10% by weight of the above-mentioned diethylphosphinic acid.

Example 8

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

The molded articles were then prepared according to the general procedure for preparing polymer molded articles using a composition of 90% by weight of bisphenol a resin with curing agent and catalyst and 10% by weight of the obtained ethylphosphonic acid.

Example 9

The moldings were produced according to the general procedure for producing polymer moldings using a composition of 90% by weight of bisphenol A resin with curing agent and catalyst and 10% by weight of a mixture according to the invention of diethylphosphinic acid and ethylphosphonic acid according to example 1.

Example 10

The moldings were produced according to the general procedure for producing polymer moldings using a composition of 90% by weight of bisphenol A resin with curing agent and catalyst and 10% by weight of a mixture according to the invention of diethylphosphinic acid and ethylphosphonic acid according to example 2.

Example 11

The moldings were produced according to the general procedure for producing polymer moldings using a composition of 90% by weight of bisphenol A resin with curing agent and catalyst and 10% by weight of a mixture according to the invention of diethylphosphinic acid and ethylphosphonic acid according to example 3.

Example 12

The moldings were produced according to the general procedure for producing polymer moldings using a composition of 90% by weight of bisphenol A resin with curing agent and catalyst and 10% by weight of a mixture according to the invention of diethylphosphinic acid and ethylphosphonic acid according to example 4.

Example 13

The moldings were produced according to the general procedure for producing polymer moldings using a composition of 90% by weight of bisphenol A resin with curing agent and catalyst and 10% by weight of a mixture according to the invention of diethylphosphinic acid and ethylphosphonic acid according to example 5.

The results are reproduced in the following table:

the values for the laminates of the substance mixtures according to the invention with diethylphosphinic acid and ethylphosphonic acid are reduced compared with the pure laminates (example 6); and therefore the thermal expansion is extremely low. An increase in the proportion of ethylphosphonic acid leads to a further improvement.

The mixtures according to the invention exhibit low values of the coefficient of thermal expansion compared with the prior art (example 6), i.e. the products according to the invention lead to moldings having a lower expansion and thus meeting the requirements for dimensional stability.

Claims (18)

1. The use of mixtures of at least one dialkylphosphinic acid of the formula (I) and at least one alkylphosphonic acid of the formula (II) as flame retardants for producing flame-retardant polymer molding materials, for producing flame-retardant polymer moldings and/or for imparting flame retardancy to polyesters and also to pure and blended cellulosic fabrics by impregnation, and as synergists,

wherein

R¹，R²Identical or different and independently of one another represent C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl radical, C₇-C₁₈An alkylaryl group;

wherein

R³Is represented by C₁-C₁₈Alkyl radical, C₂-C₁₈Alkenyl radical, C₆-C₁₈Aryl and/or C₇-C₁₈An alkylaryl group.

2. Use according to claim 1, characterized in that as flame retardants for varnishes and intumescent coatings, as flame retardants for wood and other cellulose-containing products, and as reactive and/or non-reactive flame retardants for polymers.

3. Use according to claim 1 or 2, characterized in that R¹、R²And R³Identical or different and denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl.

4. Use according to claim 1 or 2, characterized in that the mixture comprises 0.1 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 0.1 to 99.9% by weight of alkylphosphonic acids of the formula (II).

5. Use according to claim 1 or 2, characterized in that the mixture comprises from 40 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and from 60 to 0.1% by weight of alkylphosphonic acids of the formula (II).

6. Use according to claim 1 or 2, characterized in that the mixture comprises 60 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 40 to 0.1% by weight of alkylphosphonic acids of the formula (II).

7. Use according to claim 1 or 2, characterized in that the mixture comprises 80 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 20 to 0.1% by weight of alkylphosphonic acids of the formula (II).

8. Use according to claim 1 or 2, characterized in that the mixture comprises 90 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 10 to 0.1% by weight of alkylphosphonic acids of the formula (II).

9. Use according to claim 1 or 2, characterized in that the mixture comprises 95 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 5 to 0.1% by weight of alkylphosphonic acids of the formula (II).

10. Use according to claim 1 or 2, characterized in that the mixture comprises 98 to 99.9% by weight of dialkylphosphinic acids of the formula (I) and 2 to 0.1% by weight of alkylphosphonic acids of the formula (II).

11. Use according to claim 1 or 2, characterized in that the dialkylphosphinic acid is diethylphosphinic acid, ethylpropylphosphinic acid, ethylbutylphosphinic acid, ethylpentylphosphinic acid, ethylhexylphosphinic acid, dipropylphosphinic acid, propylbutylphosphinic acid, propylpentylphosphinic acid, propylhexylphosphinic acid, dibutylphosphinic acid, butylpentylphosphinic acid, butylhexylphosphinic acid, dipentylphosphinic acid, pentylhexylphosphinic acid and/or dihexylphosphinic acid; and the alkyl phosphonic acid is ethyl phosphonic acid, propyl phosphonic acid, butyl phosphonic acid, pentyl phosphonic acid, or hexyl phosphonic acid.

12. Use according to claim 1 or 2, characterized in that the mixture comprises 98 to 99.9% by weight of diethylphosphinic acid and 0.1 to 2% by weight of ethylphosphonic acid.

13. Use according to claim 1 or 2, characterized in that the mixture further comprises at least one synergist, wherein the synergist is 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; 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; carbodiimides, phosphazenes, piperazine phosphates, piperazine pyrophosphates, polyisocyanates, and/or styrene-acrylic polymers; aluminum hydroxide, halloysite, sapphire products, 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.

14. Use according to claim 1 or 2, characterized in that the mixture further comprises at least one synergist, wherein the synergist is an aluminium compound, a magnesium compound, a tin compound, an antimony compound, a zinc compound, a silicon compound, a phosphorus compound, an isocyanate, a piperazine.

15. Use according to claim 1 or 2, characterized in that the mixture further comprises at least one synergist, wherein the synergist is boehmite.

16. Use according to claim 1 or 2, characterized in that the mixture comprises 99 to 1% by weight of a mixture of dialkylphosphinic acids of the formula (I) and alkylphosphonic acids of the formula (II) as defined in claim 1 or 2 and 1 to 99% by weight of a synergist.

17. Flame-retardant thermoplastic or thermosetting polymer moulding materials, polymer mouldings, polymer films, polymer filaments and polymer fibres, comprising from 0.5 to 45% by weight of a mixture as defined in any one of claims 1 to 16, from 55 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.

18. 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 as defined in any of claims 1 to 16, from 0 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.