WO2009077796A2 - Procédé pour la préparation d'amides de l'acide phosphorique à fonctionnalité amine - Google Patents

Procédé pour la préparation d'amides de l'acide phosphorique à fonctionnalité amine Download PDF

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Publication number
WO2009077796A2
WO2009077796A2 PCT/HU2008/000145 HU2008000145W WO2009077796A2 WO 2009077796 A2 WO2009077796 A2 WO 2009077796A2 HU 2008000145 W HU2008000145 W HU 2008000145W WO 2009077796 A2 WO2009077796 A2 WO 2009077796A2
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group
amine
solvent
optionally substituted
reaction
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PCT/HU2008/000145
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English (en)
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WO2009077796A3 (fr
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Péter ANNA
György MAROSI
Andrea Toldi
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Anna Peter
Marosi Gyoergy
Andrea Toldi
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Application filed by Anna Peter, Marosi Gyoergy, Andrea Toldi filed Critical Anna Peter
Priority to EP08862519A priority Critical patent/EP2265622A2/fr
Publication of WO2009077796A2 publication Critical patent/WO2009077796A2/fr
Publication of WO2009077796A3 publication Critical patent/WO2009077796A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/224—Phosphorus triamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to a novel improved process for preparing amine functional phosphoric amides, which are useful flame retardants and curing agents especially for epoxy resins.
  • the inventive method offers a simple, cost-effective and environmentally friendly method using inexpensive starting materials.
  • Epoxy resins have found use in various industrial applications in the last 50 years since they have been commercially available, due to their excellent characteristics as toughness, chemical, mechanical and electrical resistance, low shrinkage on cure and high adhesion to many substrates. They are widely used for surface coatings, castings, laminates, adhesives, composites, potting and painting materials, especially in application areas where their technical advantages balance their higher costs compared to other thermosetting polymers, e.g. electronic and electrical industry, transportation industry.
  • the main deficiency of epoxy resins is their flammability. In order to meet application requirements their flame retardant properties have to be improved by maintaining other important characteristics as thermal and mechanical properties, and also considering environmental issues as risks for human life and environment, waste treatment and recycling.
  • halogenated epoxy components as the diglycidyl ether of tetrabromobisphenol A is a highly effective method for the preparation of flame retarded epoxy resin systems, as according to description JP57092017, however the increasing focus on the health and environmental compatibility of flame retardants has resulted in a steady decline in the acceptance of halogen-containing products. Public perception of the environmental impact of combustion of certain halogenated flame retardants during incineration has become an issue in Europe because of the possible production of dibenzodioxins and dibenzofurans.
  • organophosphorous compounds As an environmental alternative for the halogen-containing type flame retardants, organophosphorous compounds have been recognized and developed over a number of years and thus have found use as additives in a variety of polymeric materials. Many organophosphorous additives are of low molecular weight and are therefore somewhat volatile, causing their partial loss from the polymer during either high temperature processing by migration to the surface or in the early stages of combustion. Additionally, their transition into the gaseous phase may cause the smoke of the burning material to become loaded with toxic phosphorus-containing compounds. Clearly, there is a need to increase the permanence of the additive within the polymer matrix in order to maximize the fire retardancy and to reduce the evolution of toxic species.
  • the incorporation of the organophosphorus functionality within the polymeric structure may offer solution to this problem.
  • the US patent No. 3,981 ,832 discloses phosphorus-containing flame retardant additives, which are used in a mixture made of ammonium polyphosphate, pentaerythritol and melamine. Nevertheless it also has to be calculated with the disadvantages of solid additives in this case as increase in viscosity due to the large amount of flame retardant additive needed and therefore deterioration of mechanical properties.
  • Transamidation reactions are well known in peptide chemistry and generally mean the reaction between an amine and an ester or amide compound resulting in an amide. Nevertheless, there was no indication in the state of art that amine functional phosphoric amides can be prepared by a simple, cost effective reaction starting from orthophosphoric acid and di- or polyamines, the literature [O. Maurer, see above] rather suggested that by such reactions no complete replacement of the phosphate ester groups can be achieved.
  • the present invention also relates to the use of amine functional phosphoric amides prepared by the inventive process as curing agent and flame retardant in epoxy resins.
  • the invention relates to a process for the preparation of amine functional phosphoric amides according to general formula (I) which comprises reacting an orthophosphoric acid ester of general formula (II) with an amine of general formula (III) optionally in the presence of a catalyst
  • R' is an optionally substituted straight or branched aliphatic group, which can be saturated or unsaturated, or an optionally substituted aromatic group,
  • R" is a optionally substituted straight or branched aliphatic group, which can be saturated or unsaturated, or an optionally substituted aromatic group.
  • a phosphate ester of orthophosphoric acid of general formula (II) is transamidated by various diamine or polyamine compounds of general formula (II).
  • an alcohol of the general formula R'OH is produced from the starting ester, which can be evaporated from the mixture at the and of the reaction, optionally together with the solvent (if any) or with the remaining unreacted lower boiling point amine component.
  • phosphoric acid means orthophosphoric acid (H 3 PO 4 ).
  • R' is an optionally substituted straight or branched C 1 -C 18 alkyl group, a C 3 -C 6 cycloalkyl group or C 6 -C 8 aryl group, preferably a C 1 -C 8 alkyl group.
  • the further preferred groups are the methyl, ethyl, propyl or butyl groups or the phenyl, benzyl, toluyl or xilyl groups.
  • phosphate esters of general formula (II) not only symmetrically trisubstituted esters of orthosposphoric acid but mixed esters of thereof can be used as well.
  • aliphatic esters such as trimethyl phosphate, triethyl phosphate or phosphate esthers of other alcohols with short carbon chain or their mixture and further aromatic phosphate esters such as triphenyl phosphate and cycloaliphatic phosphate esters can be used advantageously. It is also within the scope of the present invention if a mixture of different phosphate esters is transamidated by the inventive process.
  • aliphatic compounds mean acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds.
  • the amine of general formula (III) can be generally a di- or a polyamine, wherein R" is an optionally substituted straight or branched aliphatic group, which can be saturated or unsaturated, or an optionally substituted aromatic group.
  • R" is an optionally substituted straight or branched C 1 -C 18 alkylene group, a C 3 -C 6 cycloalkylene group or C 6 -C 8 arylene group. In a further preferred embodiment R" is a C 1 -C 8 alkylene group, preferably a C 1 -C 6 alkylene group.
  • R" is selected from aromatic groups including phenylene, benzylene, tolylene or xilylene group or from aliphatic groups including methylene, ethylene, propylene, butylene or hexamethylene group or from aminosubsituted groups such as diethylene-amino, triethylene-diamino, dipropylene- amino, pentaethylene-tetraamino group.
  • the R" and R' groups such as alkyl, alkylene, aryl, arylene, cycloalkyl, cycloalkylene etc.
  • the amines of the general formula (III) have at least two, but optionally more than two primary amino groups in terminal position or as pendent groups in the R" residue, and they can be also positioned in a side chain if R" represents e.g. a branched chain aliphatic group, such as e.g. an alkylene group.
  • R" represents e.g. a branched chain aliphatic group, such as e.g. an alkylene group.
  • both primary diamines and primary polyamines can be in the inventive process.
  • an oxo substituted C 2 -C 8 alkylene group can be e.g. an alkoxy-alkyl group having the same number of carbon atoms.
  • Alkyl/aryl spiroborane residues and alkyl/aryl silane residues are derived from e.g. R-O- C(CO) 2 -B-O-R- and R-O-(Si-R 2 -O)-Si-O-R- groups, respectively.
  • amine compounds aliphatic diamines can be advantageously applied, such as ethylenediamine, diethylenetriamine, hexamethylenediamine; polyamines containing one or more cycloaliphatic units as 1 ,2-diamino cyclohexane, bis(paraaminocyclohexyl)methane; aromatic diamines as meta phenylenediamine, bis (paraaminodiphenyl)methane, etc. or their mixture.
  • Liquid amines are preferred because in this case no additional solvent is needed to carry out the reaction, the amine being in excess serves as a solvent per se.
  • Aromatic amines can be also advantageous because the aromatic compounds promote the formation of an intumescent char during burning, which enhances the flame retardant effect in the epoxy resin.
  • both R' and R" can be independently the same or different groups. This means that not only symmetrically trisubstituted but also mixed esters of the phosphoric acid can be used.
  • R' and R" can be independently the same or different groups. This means that not only symmetrically trisubstituted but also mixed esters of the phosphoric acid can be used.
  • a chemically homogenous mixture of di- or polyamines of the general formula (III) could be advantageous for cost or technical considerations, it is possible to use a mixture of different di- or polyamines, which lead to a non-uniformly substituted product of the general formula (I). In this latter case within one molecule of the end product of the formula (I) the R" groups can be the same or different.
  • the reaction mixture and the workflow applied differently
  • N-trisubstitued phosphoric acid amides can be prepared or a mixture of symmetrically N- trisubstituted phosphoric acid amides can be prepared as well.
  • the chemical structure of the end product of the general formula (I) can be controlled by the feed of the components, as e.g. the different amine components can be added sequentially or in a mixture of more than one di- or polyamine.
  • a catalyst is desirable to reduce the reaction time, it can be selected from the well known transesterification reactions catalysts. These include from alkali metal alcoholates, preferably from C 1 to C 18 alkali metal alcoholates, more preferably sodium ethylate; solid acid type catalysts, preferably a clay catalyst, more preferably montmorillonite, hidrotalcite or nanodispersed montmorillonit.
  • a clay catalyst such as montmorillonite, hidrotalcite or nanodispersed montmorillonit
  • the catalyst can be left in reaction mixture without any further processing as clay nanoparticles have synergistic flame retardant effect with phosphorus-containing flame retardants.
  • the use of clay catalysts can be advantageous both for the reaction both for the end product.
  • Clays are generally defined as hydrous aluminium phyllosilicates, which can have variable amounts of iron, magnesium, alkali metals, alkaline earths and other cations. Clays have structures similar to the micas. Clay minerals include the following groups: kaolinite group which includes the minerals kaolinite, dickite, halloysite and nacrite; serpentine group; smectite group which includes pyrophyllite, talc, vermiculite, sauconite, saponite, nontronite and montmorillonite; illite group which includes the clay-micas; chlorite group which includes a wide variety of similar minerals with considerable chemical variation. [Wikipedia, www.wikipedia.org] According to the invention smectite type clays, preferably montmorillonit or hydrotalcit or nanodispersed froms thereof can be used as a catalyst.
  • the reaction can be carried out in the presence of an appropriate additional solvent, preferably in a non-aqueous apolar solvent, such as toluene, benzene, xylene or hexane or in an aprotic polar solvent, such as acetone, acetonitrile or tetrahydrofurane. It is also possible to perform the reaction in the absence of an additional solvent, especially if liquid amines of the general formula (III) are used. In case of using liquid amine reagents such as ethylene diamine, no additional solvent is needed (the solvent is the amine component itself) as the excess of the liquid amine not only shifts the equilibrium of the reaction to the formation of amide and alcohol, but also serves as a solvent.
  • an appropriate additional solvent preferably in a non-aqueous apolar solvent, such as toluene, benzene, xylene or hexane or in an aprotic polar solvent, such as acetone, acetonitrile
  • the amine has to be added preferably in excess to the desired molar ratio.
  • RT room temperature
  • the person skilled in the art is able to determine the reaction conditions applicable for a certain combination of reagents and catalysts.
  • non-aqueous apolar solvents as e.g. toluene, benzene, xylene or hexane or aprotic polar solvent such as e.g. acetone, acetonitrile or tetrahydrofurane can be used as solvent, which is removed by vacuum-distillation after the reaction took part.
  • Alcohols are generally not preferred solvents as they would shifts the equilibrium of the reaction backwards.
  • the reaction can be carried out at a temperature between the melting point and the boiling point of the amine, which serves as the reaction solvent.
  • it is preferable to work at lower temperatures e.g. between 0 0 C and 150 0 C, 0 0 C and 100 0 C or more preferably between RT and 100°C. Consequently, if higher melting amines of the general formula (III) have to be used, the use of an additional solvent makes it possible to reduce the reaction temperature, and work e.g. between O 0 C and 150 0 C, 0°C and 100°C or preferably between RT and 100°C or preferably between RT and the boiling point of the additional solvent under reflux.
  • the excess of the amine can be removed by vacuum- destillation together with the formed alcohol.
  • the vacuum used for vacuum-distillation of the excess of amine or the solvent is preferably in the range of 0.1-1 Hgmm or better. Worse vacuum can lead to longer distillation process and polymerization of the end- product. If the reaction time or temperature exceeds the applicable limit, polymerization of the endproduct can occur.
  • epoxy component the traditional glycidyl ether of bisphenol A or its derivatives can be used.
  • Alkyl di and polyglycidyl ethers also known as reactive dilutants, as 1 ,4-butanol glycidyl ether, glycerine triglycidyl ether, pentaerythrite tetraglycidyl ether and others; mono glycidyl ethers as butyl glycidyl ether, phenyl glycidyl ether can be also used as components containing epoxy functionality.
  • DGEBA diglycidyl ether of bisphenol A
  • additives for epoxy resins the following additives can be considered: fillers, as silica, calcium carbonate, layered and fibrous reinforcing materials, talc, mica, nanosilicates, hidrotalcite, montmorillonite, sepiolite, glass fibre, natural and synthetic fibres and additives facilitating the application as wetting and antifoaming agents, etc.
  • the epoxy resin described in this invention can be also used together with traditional flame retardants as metal hydroxides, phosphorus-containing additives as ammonium polyphosphate, non-reactive alkyl and aryl phosphate esthers, halogen-containing additives, etc. according to the needs.
  • the advantages of the phosphorus-containing amine component described in this invention are the unchanged viscosity during the production, appropriate mechanical strength and component stability of the crosslinked resin, which can be demonstrated applying the following testing methods:
  • the fire resistance was characterized by limiting oxygen index measurement (LOI, according to ASTMD 2863), UL-94 test (according to ASTM 1356-90 and ANSI//ASTM D- 635/77, respectively), Mass Loss Calorimeter (according to ISO 13927, Fire Testing Technology, heat flux of 50 kW/m2), and Glow Wire Flammability Index test (GWFI, PTL DR. GRABENHORST, D-8652 Stadtsteinach, T03.34 type apparatus, according to IEC 60695-2-12).
  • LOI limiting oxygen index measurement
  • UL-94 test according to ASTM 1356-90 and ANSI//ASTM D- 635/77, respectively
  • Mass Loss Calorimeter accordinging to ISO 13927, Fire Testing Technology, heat flux of 50 kW/m2
  • LOI measurements were done using OXINDEX apparatus built by MUKI.
  • LOI value represents the minimum concentration of oxygen (expressed as percent by volume) in a mixture of oxygen and nitrogen that will support flaming combustion of a material that is initially at room temperature. A higher value indicates a less flammable material.
  • UL-94 test determines the material's tendency either to extinguish or to spread the flame once the specimen has been ignited. Specimens are oriented in either a horizontal or vertical position, depending on the specifications of the relevant- test method, and are subjected to a defined flame ignition source for a specified period of time. From lowest (least flame retardant) to highest (most flame retardant), the classifications are: HB: slow burning on a horizontal specimen; burning rate ⁇ 76 mm/min for thickness ⁇ 3 mm.
  • V2, V1 and VO indicate that the material was tested in a vertical position and self-extinguished within a specified time after the ignition source was removed:
  • V2 burning stops within 30 seconds on a vertical specimen; drips of flaming particles are allowed.
  • V1 burning stops within 30 seconds on a vertical specimen; no drips allowed.
  • VO burning stops within 10 seconds on a vertical specimen; no drips allowed.
  • the mass loss calorimeter measures mass loss rate, time to ignition and heat release rate during the burning of material or product specimens.
  • a radiant electrical heater in the shape of a truncated cone. This heating element irradiates a flat horizontal sample, 100 mm x 100 mm and up to 50 mm thick, placed beneath it, at a preset heating flux of up to 100 kW/m2 (in our case 50 kW/m2.).
  • the sample is placed on a load cell for continuous monitoring of its mass as it burns. Ignition can be optionally forced by an intermittent spark igniter located above the sample.
  • the glow wire flammability index (GWFI) test is used to simulate the effect of heat as may arise in malfunctioning electrical equipment, such as with overloaded or glowing components. Test results provide a way of comparing the ability of materials to extinguish flames and their ability to not produce particles capable of spreading fire.
  • the glow wire is heated via electrical resistance to a specified elevated temperature. A test specimen is held for 30 seconds against the tip of the glow wire with a force of 1 N. After the glow wire is removed, the time for the flames to extinguish is noted along with details of any burning drops. Cotton is placed beneath the specimen during the test to determine the effects of burning drops.
  • the glow wire flammability index is the highest temperature which satisfies one of the following conditions in three successive tests:
  • - burning or glowing time is less than 30 seconds after removal of the glow wire and the cotton does not ignite.
  • Glow wire temperatures 550, 600, 650, 700, 750, 800, 850, 900, 960 0 C
  • GWFI 65O 0 C for electronic appliances which cannot be left without attendance during use
  • GWFI 750°C the device can be left without attendance
  • GWFI 850 0 C even current may flow on the flame retarded part
  • GWFI 960 0 C can be used in electrical and electronic equipment for unattended use continuously loaded, or equipment to be used near the central supply point of a building; both in parts in contact with, or retaining in position current-carrying parts and in enclosures and covers not retaining current-carrying parts in position. Suitable for all kinds of electronic application.
  • Rheological characterization of the epoxy resin components was done on TA Instruments AR2000 type rheometer. The measurements were done with flow procedure applying the following parameters: parallel plate geometry, upper plate diameter: 40 mm, lower plate: Peltier plate, gap: 1000 ⁇ m, temperature: 25°C; in case of steady state flow step measurements the shear rate ranged from 1-10 1/s in 4 linear steps.
  • Shore A type hardness was determined according to the standard MSZ 13636-73.
  • the Shore durometer measures the depth of an indentation in the material created by a given force on a standardized presser foot.
  • the value of the hardness (ranging from 0 to 100, with higher values indicating a harder material) depends on the depth of the indenter's penetration.
  • the extraction test was carried out to demonstrate the component stability of the cured epoxy resin.
  • the extraction was done by Soxhlet-extractor using 350 cm3 benzine (boiling point in the region of 80-110 0 C) as extraction solvent, the turn over ratio of the solvent was 5 and the mass of the cured epoxy resin was 10 g.
  • the mass loss of the dried sample is characteristic for the component stability of the resin: the smaller the mass loss is, the higher is the component stability.
  • example 4 and 5 serve as comparative examples, while example 6 and 7 make use of the amine functional phosphoric amide flame retardant prepared according to the present invention.
  • the first comparative sample consists of AH-16 epoxy component and T-58 curing agent without any flame retardants.
  • Eporezit AH-16 epoxy resin was applied with Eporezit T-58 curing agent, supplied by P+M
  • sample 3 appropriate amounts according to Table 1 of AH-16 epoxy component and T-58 hardener were mixed in a glass beaker by a glass rod for one minute. After homogenization viscosity measurements where done from the mixture and from the rest of it 15 mm x 125 mm x 3mm and 100 mm x100 mm x3mm samples were made for flame retardancy tests, mechanical characterization and extraction test, which were done after 1 week of curing at room temperature. The properties of the sample are given in Table 1.
  • Example 4 is also a comparative sample consisting of AH-16 epoxy component, T-58 curing agent and an additive flame retardant according to the compositions described in Table 1. The properties of the sample are also given in Table 1.
  • Example 6 made according to this invention serves to demonstrate the advantages of the flame retarded epoxy resin made with amine functional phosphoric amide flame retardant.
  • the phosphoric amine applied in this example was synthesized according to the following method: To 9.3 ml (0.055 mol) of P(O)(OEt)3 36.7 ml (0.55 mol) of H2N-CH2CH2-NH2 was added and the mixture was stirred at the boiling point of H2N-CH2CH2-NH2, at 118°C for 3 hours. Instead of the necessary 3 equivalents of H2N-CH2CH2-NH2 10 equivalents were used in order to shift the equilibrium in the direction of the required trisubstituted product.
  • Example 7 is also a sample according to the invention, which serves to demonstrate the advantages of the flame retarded epoxy resin made with amine functional phosphoric amides flame retardant.
  • the curing agent used in this sample was synthesized as described in Example 3.
  • the amine number, determined according to the method described in case of Example 6, was 450+5 mg KOH/g.
  • the epoxy resin sample was made from the amine synthesized according to this example, according to the composition listed in Table 1 and method described in case of Example 4. The properties of this sample are summarized in Table 1. Summary of the results
  • the epoxy resins flame retarded this way reach LOI value 40 and V-O UL-94 rating, 960 °C GWFI value compared to the LOI value of 21 , HB UL-94 rating and 550 0 C GWFI value of the reference epoxy resin.
  • the peak of the heat release rate measured by Cone calorimeter is reduced to its 1/10 compared to non flame retarded epoxy resin, furthermore a shift in time can be observed, which reduces the time to escape in case of fire event.
  • the epoxy resins flame retarded by these amine functional phosphoric amides are appropriate for all electronic appliances, the GWFI value of 960 0 C means that they can be used in equipment for unattended use continuously loaded under stringent conditions. Varying the ratio of the not phosphorus- containing curing agent and the phosphorus-containing one every demand for flame retardancy can be fulfilled cost-effectively.
  • the amine functional phosphoric amide compound acts as flame retardant similarly as the so called intumescent additive systems: during the high temperature ignition phosphorous oxide is formed on the surface of the polymer, which abstracts water from the structure of the epoxy resin and forms a phosphorocarbonaceous layer on the surface blown up by the evolved nitrogen-containing gases from the decomposed amine parts of the matrix.
  • the so formed intumescent layer protects the rest of the resin from the ignition source, hinders the leaving of flammable gases from the incalescent resin and the mixing of these flammable gases with the oxygen of the environment.
  • the process provided by the present invention makes possible to produce different amine functional phosphoric amides of the general formula (I) for use in epoxy resins. These compounds contain phosphorous and can be used both as crosslinking agent and as reactive flame retardant.
  • the inventive transamidation synthesis is a cost-effective and environmentally-friendly, simple way to prepare said amine functional phosphoric amides from phosphate esters and di or polyamines.
  • the invention is thus of great advantage to epoxy resin products that should satisfy high standards of security, especially inflammability in e.g. automotive parts and housings.
  • the synthesized amines can substitute the traditional epoxy resin curing agents additionally providing excellent flame retardancy: the epoxy resins flame retarded this way have an LOI value of 39% and V-O UL-94 rating, 960 0 C GWFI value and also the peak of the heat release rate measured by Cone calorimeter is reduced to its 1/10 compared to non flame retarded epoxy resin.
  • the synthesized amines contain 5-15 mass% of phosphorus.
  • the traditional curing agent can be replaced partially or fully by them. In case of full replacement about 25-35 mass% of the phosphorus-containing amine is needed, which means that the epoxy resin composition contains 2.5-4.5% of phosphorus, which provides an excellent flame retardant effect.
  • the mechanical properties of the cured resin are as good as of the original resin.

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Abstract

La présente invention concerne un nouveau procédé amélioré pour préparer des amides de l'acide phosphorique à fonctionnalité amine, lesquels sont des retardateurs de flamme et des durcisseurs utiles, en particulier pour des résines époxydes. Le procédé de l'invention offre un procédé simple, économiquement rentable et respectueux de l'environnement, utilisant des matières de départ bon marché.
PCT/HU2008/000145 2007-12-07 2008-12-05 Procédé pour la préparation d'amides de l'acide phosphorique à fonctionnalité amine WO2009077796A2 (fr)

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EP08862519A EP2265622A2 (fr) 2007-12-07 2008-12-05 Procédé pour la préparation d'amides de l'acide phosphorique à fonctionnalité amine

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HU0700792A HUP0700792A2 (en) 2007-12-07 2007-12-07 Process for the preparation of amine functional phosphoric amides and their use as flame retardant and curing agent for epoxy resing
HUP0700792 2007-12-07

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WO2009077796A2 true WO2009077796A2 (fr) 2009-06-25
WO2009077796A3 WO2009077796A3 (fr) 2009-08-13

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WO2016166229A1 (fr) 2015-04-17 2016-10-20 Alzchem Ag Durcisseurs et accélérateurs de durcissement à effet ignifuge pour le durcissement de résines époxy (ii)
CN106519297A (zh) * 2016-11-11 2017-03-22 青岛科技大学 一种阻燃剂的胺解合成方法及磷氮阻燃剂
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CN108892780A (zh) * 2018-05-31 2018-11-27 江苏邦杰防腐保温科技有限公司 一种耐高温有机硅磷酸酯树脂及其制备方法、耐高温涂料及其制备方法
CN110003488A (zh) * 2019-04-16 2019-07-12 西北工业大学 一种双亲性聚集诱导发光超支化聚磷酰胺及合成方法
CN116903962A (zh) * 2023-09-14 2023-10-20 汕头市贝斯特科技有限公司 一种复合型阻燃母粒及其应用

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016166229A1 (fr) 2015-04-17 2016-10-20 Alzchem Ag Durcisseurs et accélérateurs de durcissement à effet ignifuge pour le durcissement de résines époxy (ii)
WO2016166226A1 (fr) 2015-04-17 2016-10-20 Alzchem Ag Durcisseur et accélérateur de durcissement avec effet retardateur de flamme pour le durcissement de résines époxydes
DE102016004590A1 (de) 2015-04-17 2016-11-03 Alzchem Ag Härter und Härtungsbeschleuniger mit Flammschutzwirkung zur Härtung von Epoxidharzen (II)
DE102016004605A1 (de) 2015-04-17 2016-11-03 Alzchem Ag Härter und Härtungsbeschleuniger mit Flammschutzwirkung zur Härtung von Epoxidharzen (I)
CN106519297A (zh) * 2016-11-11 2017-03-22 青岛科技大学 一种阻燃剂的胺解合成方法及磷氮阻燃剂
CN108659204A (zh) * 2018-01-10 2018-10-16 苏州巨峰电气绝缘系统股份有限公司 一种含磷、氮无卤阻燃环氧绝缘树脂及其制备方法
CN108659204B (zh) * 2018-01-10 2020-08-14 苏州巨峰电气绝缘系统股份有限公司 一种含磷、氮无卤阻燃环氧绝缘树脂及其制备方法
CN108485351A (zh) * 2018-04-23 2018-09-04 武汉工程大学 一种基于改性水滑石的水性抑烟膨胀型防火涂料及其制备方法
CN108892780A (zh) * 2018-05-31 2018-11-27 江苏邦杰防腐保温科技有限公司 一种耐高温有机硅磷酸酯树脂及其制备方法、耐高温涂料及其制备方法
CN110003488A (zh) * 2019-04-16 2019-07-12 西北工业大学 一种双亲性聚集诱导发光超支化聚磷酰胺及合成方法
CN116903962A (zh) * 2023-09-14 2023-10-20 汕头市贝斯特科技有限公司 一种复合型阻燃母粒及其应用
CN116903962B (zh) * 2023-09-14 2023-12-01 汕头市贝斯特科技有限公司 一种复合型阻燃母粒及其应用

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