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WO2020177559A1 - 二烷基次膦酸-烷基亚磷酸金属复合盐及制备方法和用途 - Google Patents

二烷基次膦酸-烷基亚磷酸金属复合盐及制备方法和用途 Download PDF

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Publication number
WO2020177559A1
WO2020177559A1 PCT/CN2020/076237 CN2020076237W WO2020177559A1 WO 2020177559 A1 WO2020177559 A1 WO 2020177559A1 CN 2020076237 W CN2020076237 W CN 2020076237W WO 2020177559 A1 WO2020177559 A1 WO 2020177559A1
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Prior art keywords
acid
flame retardant
mixture
salt
metal composite
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PCT/CN2020/076237
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English (en)
French (fr)
Inventor
黎少桦
Original Assignee
黎杰
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Priority to EP20764930.2A priority Critical patent/EP3964517A4/en
Publication of WO2020177559A1 publication Critical patent/WO2020177559A1/zh

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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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the invention relates to a metal composite salt of dialkylphosphinic acid-alkylphosphinic acid and/or a mixture thereof, and a preparation method and application thereof.
  • the present invention relates to a halogen-free flame retardant of a dialkylphosphinic acid-alkyl phosphite metal composite salt, as a flame retardant synergist, and a preparation method and application thereof.
  • polymer materials such as polyolefin, polyester, polycarbonate, polyamide, polyurethane, epoxy resin, polyacrylate, and various other types of thermoplastic or thermosetting plastic molding compounds, elastomer materials, coatings, Synthetic fibers are generally relatively flammable materials.
  • products made with these materials in many cases need to meet certain flame retardant standards.
  • flame retardants such as bromine-containing compounds and phosphorus-containing compounds, can usually be added to the formulation of these materials. Flame retardant composed of the compound.
  • Phosphorus-containing compound flame retardants are welcomed by the market because of their relatively high flame retardant efficiency and less smoke generated when materials are burned, and have become the development trend of the flame retardant industry in recent years.
  • Most phosphorus-containing compounds such as phosphoric acid ester flame retardants, because of their low decomposition temperature, mobility in materials and greater volatility, limit their application in plastics, especially engineering plastics.
  • One of the high temperature flame retardants that can be applied to engineering plastics is dialkyl phosphinate.
  • Patent DE19752735 discloses a method for the synthesis of dialkylphosphinates.
  • Patent CN103951699B discloses a method for synthesizing aluminum diethylphosphinate to increase the reaction rate.
  • Patent DE2447727 discloses an application method using organic phosphinate and organic bisphosphinate.
  • dialkyl aluminum phosphinate and zinc dialkyl phosphinate have been recognized by the market as flame retardants and have been commercialized products.
  • aluminum diethylphosphinate as an environmentally friendly halogen-free flame retardant, has been widely used in plastics, leather, electronic circuit boards and other fields.
  • the efficiency of using aluminum diethyl phosphinate alone is generally not high.
  • US6365071B1 discloses a compounding technology of aluminum alkyl phosphinate and melamine cyanuric acid.
  • Patent US6255371B1 discloses the combination of aluminum diethylphosphinate and melamine. Phosphoric acid compounding technologies, these compounding technologies greatly improve the efficiency of the flame retardant system, and also reduce the cost of materials. However, these compound systems often cause polymer degradation during high-temperature processing, resulting in deterioration of the mechanical properties of the material, and at the same time, because of their own characteristics, they often cause a certain degree of corrosion to the production equipment.
  • Patent application US20070029532A1 is for phosphorus-containing flame retardants. The decomposition of high temperature processing and the degradation of polymers and corrosion of equipment are also described in detail. To solve these problems, engineers often add other synergists that do not contain nitrogen.
  • Patent US6547992B1 discloses a composite technology of diethyl aluminum hypophosphite and zinc borate as stabilizers, which can reduce the degradation effect of flame retardants on polymers. Specially treated aluminum phosphite is also considered to be one of the effective synergists without nitrogen.
  • Patent application US2014/0336325A1 discloses a high temperature resistant aluminum phosphite compounding technology. The above-mentioned synergist compounding technology has alleviated the problems of processing or materials to a certain extent, but these synergists are used through physical mixing, and the added amount is high, and the flame retardant efficiency often still fails to meet the requirements.
  • the dialkylphosphinic acid-alkyl phosphite metal composite salt of the present invention can reduce the damage to the material performance when used as a flame retardant or a flame retardant synergist. Corrosion to equipment.
  • the dialkyl phosphinic acid-alkyl phosphite metal composite salt involved in the present invention has corresponding components in a certain molar ratio that are combined with each other in a bonding manner.
  • the present invention also relates to the mixture of the dialkylphosphinic acid-alkyl phosphite metal composite salt of the above invention.
  • dialkylphosphinic acid-alkyl metal phosphite composite salts are different from physical mixtures, because the components of the dialkylphosphinic acid-alkyl metal phosphite composite salts are not added by mixing, but by The reaction mixture of the preparation method remains in the product.
  • the inventors have discovered through research that such dialkylphosphinic acid composite metal salt or dialkylphosphinic acid-alkyl phosphite metal composite salt has more advantages in glass fiber reinforced materials such as PBT, nylon 66, and nylon 6T/66.
  • flame-retardant molding materials prepared with dialkylphosphinic acid-alkyl phosphite metal salt greatly reduce the decomposition of polymer molecules during processing, and also significantly improve the corrosion of equipment during processing .
  • An object of the present invention is to provide a halogen-free flame retardant of dialkylphosphinic acid-alkylphosphinic acid metal composite salt and a synergist used in combination with other flame retardants for the manufacture of various flame retardants Molding compounds, flame-retardant thermosetting plastics, flame-retardant coatings, flame-retardant fibers, flame-retardant leather, etc., have good flame-retardant efficiency and maintain the mechanical properties of the material, reducing the corrosion of production equipment during processing.
  • Another object of the present invention is to provide a method for preparing a dialkylphosphinic acid-alkylphosphinic acid metal composite salt.
  • Another object of the present invention is to provide a composition of a dialkylphosphinic acid-alkylphosphinic acid metal composite salt and a thermoplastic or thermosetting polymer for preparing flame-retardant products of the polymer.
  • the dialkylphosphinic acid-alkyl phosphite metal composite salt of the present invention is used as a flame retardant and a flame retardant synergist.
  • the flame retardant or flame retardant synergist of the composite salt is more
  • the dialkyl phosphinate has better flame retardant effect, can reduce the degradation of the polymer during processing and reduce the corrosion of equipment.
  • the flame retardant of the present invention can be used alone, or can be used as a flame retardant synergist together with the flame retardant in a flame retardant mixture.
  • the flame retardant mixture is mixed with other polymer additives through kneading and extrusion with the polymer to be flame-retarded.
  • the resulting polymer mixture is flame-retardant and is usually further processed later into polymer molding materials or polymer shaped bodies, etc.
  • the processing is carried out at a temperature at which the polymer exists in molten form and can significantly exceed 320°C in a short time.
  • the flame retardant synergist must be able to withstand this temperature without decomposition.
  • diethylphosphinic acid-alkylphosphonite metal composite salt when the composite salt contains a small amount of alkyl phosphite component, as a plastic flame retardant or flame retardant synergist composite salt than the corresponding simple Diethyl phosphinate has a more efficient flame retardant efficiency, reduces the degradation of polymers and reduces the corrosion of processing equipment.
  • dialkylphosphinic acid-alkyl phosphite metal composite salt involved in the present invention overcomes the deficiencies of the prior art, and is characterized in that its chemical formula is:
  • R1, R2, R3 are the same or different and are H, or linear or branched C1-C8 saturated alkyl, or linear or branched C2-C12 unsaturated alkenyl or C6-C18 aryl, or contain carboxyl group , Hydroxy, amino, ester, amide, epoxy, or halogenated organic groups.
  • M is Ca, Mg, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Al, Sr, Mn metal cations and/or protonated nitrogen bases.
  • n is the valence number of the metal cation
  • x is any number from 0 to (m-0.01)
  • y is any number from 0.0005 to (m/2),
  • the total number of metal cations M is equal to the total number of dialkylphosphinic acid-alkylphosphinic acid anions.
  • x is any number from 1 to (m-0.01)
  • y is any number from 0.0005 to (m-1)/2.
  • x is any number from 1.6 to (m-0.01)
  • y is any number from 0.0005 to (m/2-0.8).
  • the dialkylphosphinic acid-alkyl phosphite metal composite salt involved in the present invention has a particle size of 0.1 to 1000 ⁇ m, a solubility in water of 0.01 to 10 g/l, a bulk density of 80 to 800 g/l, and 0.1 To 5% residual moisture.
  • the object of the present invention is also achieved by providing a method for preparing a dialkylphosphinic acid-metal alkyl phosphite composite salt.
  • the preparation method includes the following steps:
  • the mixture of dialkyl phosphinic acid or alkali metal salt of dialkyl phosphinic acid and alkali metal salt of alkyl phosphorous acid or alkyl phosphorous acid is subjected to metathesis reaction with the aqueous solution of the metal compound in the aqueous medium solution to obtain the corresponding Dialkylphosphinic acid-metal alkyl phosphite composite salt.
  • the metal compounds include Mg, Ca, Zn, Al, Ti, Fe, Sn, Zr.
  • the aqueous medium solution here contains 50 to 100% water and 0 to 50% reaction adjustment additives.
  • the aqueous medium solution contains 80 to 100% water and 0 to 20% reaction adjustment additives.
  • the reaction adjustment additives here include inorganic acids, acid salts, carbonic acid, alkalis, and electrolytes.
  • the aqueous medium solution contains 95 to 100% water and 0 to 5% reaction adjustment additives.
  • the dialkyl hypophosphite is an alkali metal salt, especially its sodium salt.
  • the equivalent ratio of the alkali metal dialkylphosphinate-alkali metal phosphite mixture to the metal compound used is 1.5:1 to 1:2, preferably, dioxane
  • the equivalent ratio of the alkali metal hypophosphite-alkali metal phosphite mixture to the metal compound used is 1.2:1 to 1:1.2.
  • the metal compound of the above preparation method is a metal compound of Mg, Ca, Zn, Al, Ti, Sn, Zr.
  • dialkylphosphinic acid-alkyl phosphite metal composite salt is preferably diethylphosphinic acid-ethyl aluminum phosphite, diethylphosphinic acid-zinc ethyl phosphinate, diethyl Phosphinic acid-ethylmagnesium phosphite, diethylphosphinic acid-calcium ethylphosphinate, diethylphosphinic acid-aluminum phosphite, diethylphosphinic acid-magnesium phosphite, diethyl Phosphinic acid-zinc phosphinate, diethyl phosphinic acid-calcium phosphinate, diethyl phosphinic acid-titanium phosphinate.
  • the ratio of dialkyl phosphinic acid/alkyl phosphite of the dialkyl phosphinic acid-alkyl phosphite metal composite salt of the present invention can be prepared by chemical synthesis according to requirements.
  • the dialkylphosphinic acid-alkyl phosphite metal composite salt of the present invention is used as a flame retardant and a flame retardant synergist, and is mainly used for the flame retardant of engineering plastics, especially polyester PBT, polyamide PA6, PA66, PA6T/66 etc.
  • the corresponding flame-retardant engineering plastic products can be obtained by heating extrusion/injection molding.
  • the present invention also provides an application of a molding composition containing a dialkylphosphinic acid-alkyl phosphite metal composite salt as a flame retardant and an engineering plastic as a flame retardant synergist in a flame retardant thermoplastic engineering plastic .
  • the flame-retardant polymer molding compound composition preferably consists of the following components:
  • a component 55-99.9 weight percent polymer resin, preferably 60-95% polymer resin,
  • B component 0-55 weight percent reinforcing filler, preferably 1-50 weight percent reinforcing filler,
  • C component 0.1-45 weight percent of the flame retardant composition, preferably 1-35 weight percent of the flame retardant mixture,
  • the total weight percentage of each component of the flame-retardant polymer molding compound composition is 100%.
  • the flame retardant mixture contains a dialkylphosphinic acid-phosphorous acid composite salt or a mixture thereof, and at least one flame retardant synergist.
  • the flame retardant synergist is a condensation polymer of melamine, a reaction product of melamine and phosphoric acid, a reaction product of melamine and polyphosphoric acid, a reaction product of melamine and urethane cyanic acid, and/or a mixture thereof.
  • the flame retardant mixture may be a flame retardant and dialkylphosphinic acid-phosphite as a flame retardant.
  • the flame retardant includes melam, melem, double melamine pyrophosphate, melamine polyphosphate and their mixtures, ammonium phosphate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, aluminum hypophosphite, zinc hypophosphite , Calcium hypophosphite, magnesium hypophosphite, sodium phosphite, phenyl hypophosphorous acid and its metal salt, dialkyl hypophosphorous acid and its salt, monoalkyl hypophosphorous acid and its salt, propylene carboxyl hypophosphorous acid and its salt, benzene Allyl carboxyl hypophosphorous acid and its salts, aryl allyl carboxyl hypophosphorous acid and its salts, phosphaphenanthrene compound (DOPO) and its salts, benzoquinone condensation polymer
  • dialkylphosphinic acid-alkyl phosphite metal composite salt of the present invention can be further illustrated by the following examples. However, the scope of rights of the present invention is not limited to the listed cases.
  • the flame retardant and polymer chips are mixed with the ratio in Table 1, and then stretched, water-cooled, and pelletized in a temperature range of 280°C with a twin-screw pelletizer.
  • the flame retardant polymer is cut into pellets, dried, and then injection molded at 285°C using a single-screw injection molding machine.
  • Flame retardant test Perform vertical flame retardant test according to UL94 standard.
  • melt index test The influence of flame retardants on the processing of polymer materials can be evaluated by the melt index of injection molded samples. The higher the melt index of the material, the more serious the molecular decomposition of the material during the processing, which will affect the mechanics of the material. The performance is more unfavorable.
  • the test condition of the melt index is 275°C/2.16kg.
  • the flame retardant grade test of the sample is carried out according to the UL94 combustion standard, and the sample thickness is 1.6mm. According to the UL94 test result, the flame retardant material can be classified according to the following conditions:
  • V0 The flame goes out within 10 seconds after the spline leaves the fire, and there is no droplet.
  • V1 The flame goes out within 30 seconds after the spline leaves the fire, and the droplet does not ignite the cotton ball below.
  • V2 The flame goes out within 30 seconds after the spline leaves the fire, and the droplet ignites the cotton ball below.
  • Equipment corrosion index test The corrosion of the flame retardant to the equipment during the processing can be expressed by the corrosion index. The higher the corrosion index, the more severe the corrosion of the equipment during the processing.
  • the equipment corrosion index is composed of a module with a 12x15x3mm extrusion port installed in the die of the injection molding machine. After 25 kg of molding compound is injected through this module at a certain temperature, the weight loss of the die is detected.
  • Example 6 From the results in Table 1, it can be seen that the flame retardant efficiency of using aluminum diethylphosphinate alone is not high.
  • Example 6 only reached the flame retardant level of V1 when the same 20% flame retardant was added.
  • MPP melamine polyphosphoric acid

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

本发明公开一种如式(1)的二烷基次膦酸-烷基亚磷酸金属复合盐和/或其混合物的阻燃剂和阻燃协效剂，其制备方法和其作为阻燃剂和阻燃协效剂在热塑性和热固性高分子材料模塑料，涂料，纺丝和纺织品中的应用。

Description

二烷基次膦酸-烷基亚磷酸金属复合盐及制备方法和用途 技术领域
本发明涉及一种二烷基次膦酸-烷基亚膦酸的金属复合盐和/或其混合物及其制备方法和用途。具体的说本发明涉及一种二烷基次膦酸-烷基亚磷酸金属复合盐的无卤阻燃剂和作为阻燃协效剂及其制备方法和用途。
背景技术
大部分聚合物材料，比如聚烯烃，聚酯，聚碳酸酯，聚酰胺，聚氨酯，环氧树脂，聚丙烯酸酯，以及各种其他类型的热塑或热固性塑料模塑料，弹性体材料，涂料，合成纤维等，一般都是比较易燃的材料。为了安全的目的很多情况下用这些材料制造的制品需要符合一定阻燃标准，为了达到这些阻燃标准通常可以在这些材料的配方里添加一定比例的阻燃剂，比如含溴的化合物和含磷的化合物构成的阻燃剂。含磷化合物阻燃剂，因为相对阻燃效率高，材料燃烧时产生的烟雾少而受到市场的欢迎，成为近年阻燃剂行业发展的趋势。大多数含磷化合物如磷酸酯类的阻燃剂，因为其分解温度低，在材料中有迁移性和具有较大的挥发性，使其在塑料特别是工程塑料中的应用受到限制。而能适用于工程塑料的耐高温阻燃剂之一是二烷基次膦酸盐。专利DE19752735公开了一种二烷基次膦酸盐的合成方法。专利CN103951699B公开了一种提高反应速度的合成二乙基次膦酸铝的方法。专利DE2447727公开了一种使用有机次膦酸盐和有机双次膦酸盐的应用方法。根据现有技术，二烷基次膦酸铝和二烷基次膦酸锌作为阻燃剂已经得到了市场的认可，已经商业化的产品。特别是二乙基次膦酸铝，作为环保无卤阻燃剂已被大量用于塑料，皮革，电子线路板等领域。但二乙基次膦酸铝单独使用一般效率不高，为此US6365071B1公开了一种烷基次膦酸铝与三聚氰胺氰尿酸的复配技术，专利US6255371B1公开了二乙基次磷酸铝与三聚氰胺聚磷酸的复配技术，这 些复配技术大大提高了阻燃体系的效率，也降低了材料的成本。但是，这些复配体系在高温加工过程往往会导致聚合物降解，造成材料的机械性能恶化，同时因为其自身特性常常会对生产设备造成一定程度的腐蚀，专利申请书US20070029532A1对含磷阻燃剂在高温加工过程的分解和对聚合物的降解和设备的腐蚀也做了详细的描述。为解决这些问题工程师们常常会加入其他不含氮的协效剂进行使用。专利US6547992B1公开了一种二乙基次磷酸铝与硼酸锌作为稳定剂的复配技术，能够降低阻燃剂对聚合物的降解作用。经过特别处理的亚磷酸铝也被认为是不含氮的有效的协效剂之一，专利申请书US2014/0336325A1公开了一种耐高温的亚磷酸铝的复配技术。上述协效剂复配技术在一定程度上缓解了加工或材料的问题，但是这些协效剂都是通过物理混合进行使用，添加量较高，阻燃效率往往还是未能满足要求。
本发明人在研究中惊讶的发现，本发明的二烷基次膦酸-烷基亚磷酸金属复合盐作为阻燃剂或阻燃协效剂时，能够减少对材料性能的破坏，也降低了对设备的腐蚀。与现有技术不同，本发明涉及的二烷基次膦酸-烷基亚磷酸金属复合盐，其相应组分以一定的摩尔比例在本体中以键合的方式相互结合。本发明还涉及上述发明的二烷基次膦酸-烷基亚磷酸金属复合盐的混合物。这些二烷基次膦酸-烷基亚磷酸金属复合盐的混合物与物理混合物不同，因为其中二烷基次膦酸-烷基亚磷酸金属复合盐各组分并非通过混合来添加，而是由所述制备方法的反应混合物存留于产物中。本发明者经过研究发现，这样的二烷基次膦酸复合金属盐或二烷基次磷酸-烷基亚磷酸金属复合盐在PBT，尼龙66，尼龙6T/66等玻纤增强材料里具有更高的阻燃效率，用二烷基次膦酸-烷基亚磷酸金属盐制备的阻燃模塑材料大大降低了加工过程对聚合物分子的分解，也显著的改善了加工过程对设备的腐蚀。
发明内容
本发明的一个目的是提供一种二烷基次膦酸-烷基亚膦酸金属复合盐的 无卤阻燃剂和与其他阻燃剂组合使用的协效剂，用于制造各种阻燃模塑料，阻燃热固性塑料，阻燃涂料，阻燃纤维，阻燃皮革等，具有良好的阻燃效率和保持材料的机械性能，减少在加工过程中对生产设备的腐蚀。
本发明的另外一个目的是提供一种制备二烷基次膦酸-烷基亚膦酸金属复合盐的方法。
本发明的还有一个目的是提供一种二烷基次膦酸-烷基亚膦酸金属复合盐与热塑或热固性聚合物的组合物，用于制备该聚合物的阻燃制品。
令人惊奇地发现，本发明的二烷基次膦酸-烷基亚磷酸金属复合盐作为阻燃剂和阻燃协效剂，该复合盐该阻燃剂或阻燃剂协效剂比单纯的二烷基次膦酸盐有更好的阻燃功效，能够减少在加工时对聚合物的降解作用和降低对设备的腐蚀。本发明所述阻燃剂可以单独使用，也可以作为阻燃协效剂与阻燃剂一起在阻燃剂混合物中使用。通常，将所述阻燃剂混合物与其它聚合物添加剂一起通过捏合和挤出与待阻燃处理的聚合物混合。所产生的聚合物混合物是阻燃的并且稍后通常进一步加工成聚合物模塑材料或聚合物成形体等。该加工过程在这样的温度下进行，在该温度下所述聚合物以熔化形式存在并且可以短时间内显著超过320℃。阻燃剂协效剂必须能耐受该温度而不分解。令人惊奇的是现已发现，本发明的二烷基次膦酸-烷基亚磷酸金属复合盐与二烷基次膦酸铝和烷基亚磷酸铝混合物相比更加稳定，效率更高。
上述二乙基次膦酸-烷基亚膦酸金属复合盐，当复合盐含有少量的烷基亚磷酸组分时，作为塑料阻燃剂或者阻燃剂协效剂复合盐比相应的单纯的二乙基次膦酸盐具有更加高效的阻燃效率，减少对聚合物的降解作用和降低对加工设备的腐蚀。
因此，本发明涉及的二烷基次膦酸-烷基亚磷酸金属复合盐，克服了现有技术的不足，其特征在于其化学式为：
Figure PCTCN2020076237-appb-000001
其中R1，R2，R3相同或不同，为H，或直链或支链的C1-C8饱和烷基，或直链或支链C2-C12不饱和烯基或C6-C18芳基，或含有羧基，羟基，胺基，酯基，酰胺基，环氧基，或者卤代的有机基团。
其中M为Ca，Mg，Sb，Sn，Ge，Ti，Zn，Fe，Zr，Ce，Al，Sr，Mn金属阳离子和/或质子化的氮碱。
其中
m为金属阳离子的离子价位数，
x为0至(m-0.01)的任意数，
y为0.0005至(m/2)的任意数，
其中金属阳离子M的价位总数与二烷基次膦酸-烷基亚膦酸阴离子价位总数相等。
优选地，
x为1至(m-0.01)的任意数，
y为0.0005至(m-1)/2的任意数。
特别优选地，
x为1.6至(m-0.01)的任意数，
y为0.0005至(m/2-0.8)的任意数。
优选地，本发明涉及的二烷基次膦酸-烷基亚磷酸金属复合盐具有0.1至1000μm的粒子尺寸，0.01至10g/l的在水中的溶解度，80至800g/l的堆密度和0.1至5％的残留水分。
本发明的目的还通过提供制备二烷基次膦酸-烷基亚磷酸金属复合盐的方法得以实现，制备方法包括下面步骤：
将二烷基次膦酸或二烷基次膦酸碱金属盐和烷基亚磷酸或烷基亚磷酸的碱金属盐的混合物，在水介质溶液中与金属化合物的水溶液进行复分解反应，得到相应的二烷基次膦酸-烷基亚磷酸金属复合盐。其中的金属化合物包括Mg，Ca，Zn，Al，Ti，Fe，Sn，Zr。这里的水介质溶液是包含50至100％的水和0至50％的反应调节添加剂。优选地，水介质溶液是包含80至100％的水和0至20％的反应调节添加剂。这里的反应调节添加剂包含无机酸，酸性盐，碳酸，碱，电解质。
优选地，水介质溶液是包含95至100％的水，0至5％的反应调节添加剂。
优选地，二烷基次磷酸盐是碱金属盐，特别是其钠盐。
优选地，上述制备方法的复分解反应中二烷基次膦酸碱金属盐-烷基亚磷酸碱金属盐混合物与采用的金属化合物的当量比为1.5：1至1：2，优选地，二烷基次磷酸碱金属盐-烷基亚磷酸碱金属盐混合物与采用的金属化合物的当量比为1.2：1至1：1.2。
优选地，上述制备方法的金属化合物为Mg，Ca，Zn，Al，Ti，Sn，Zr的金属化合物。
上述二烷基次膦酸-烷基亚磷酸金属复合盐，优选地，为二乙基次膦酸-乙基亚磷酸铝，二乙基次膦酸-乙基亚膦酸锌，二乙基次膦酸-乙基亚磷酸镁，二乙基次膦酸-乙基亚膦酸钙，二乙基次膦酸-亚膦酸铝，二乙基次膦酸-亚磷酸镁，二乙基次膦酸-亚膦酸锌，二乙基次膦酸-亚膦酸钙，二乙基次膦酸-亚膦酸钛。
本发明的二烷基次膦酸-烷基亚磷酸金属复合盐的二烷基次膦酸/烷基亚磷酸的的比例，可根据要求通过化学合成的方式制备。
本发明的二烷基次膦酸-烷基亚磷酸金属复合盐作为阻燃剂和阻燃剂协效剂，主要用于工程塑料的阻燃，特别是聚酯PBT，聚酰胺PA6，PA66，PA6T/66等。用本发明的二烷基次膦酸-烷基亚磷酸金属复合盐与聚合物工程塑料复 配的组合物，可以通过加热挤出/注射成型得到相应的阻燃工程塑料制品。
本发明还提供了一种包含二烷基次膦酸-烷基亚磷酸金属复合盐作为阻燃剂和作为阻燃协效剂的工程塑料的模塑组合物在阻燃热塑性工程塑料中的应用。
阻燃聚合物模塑料组合物，优选地，由下列组分构成：
A组分：55-99.9重量百分比的聚合物树脂，优选地，60-95％的聚合物树脂，
B组分：0-55重量百分比的增强填料，优选地，1-50重量百分比的增强填料，
C组分：0.1-45重量百分比的阻燃剂组合物，优选地，1-35重量百分比的阻燃剂混合物，
D组分：0-30总量百分比的稳定剂和其他助剂，优选地，1-20重量百分比的稳定剂和其他助剂。
阻燃聚合物模塑料组合物各组分重量百分比的总合为100％。
优选地，阻燃剂混合物含有二烷基次膦酸-亚磷酸复合盐或其混合物，和至少一个阻燃协效剂。优选地，阻燃协效剂为三聚氰胺的缩聚物，三聚氰胺与磷酸的反应物，三聚氰胺与多聚磷酸的反应产物，三聚氰胺与尿氰酸的反应缩聚产物，和/或它们的混合物。如式(NH 4) yH 3-yPO 4或(NH 4PO 3) z,其中y＝1-3，z＝1-10,000的含氮和磷的化合物，异氰尿酸三羟乙基酯，三聚氰胺，三聚氰胺尿酸酯，双氰胺，硫氰酸胍，氧化镁，氧化钙，氧化铝，氧化锰，氧化锡，氢氧化铝，氢氧化镁，勃琅石，水滑石，水铝钙石，氢氧化钙，氢氧化锌，氧化锡水合物，硼酸锌，锡酸锌，硅酸锌盐。
选择性地，阻燃剂混合物可由一种阻燃剂和作为阻燃协二烷基次膦酸-亚磷酸盐。优选地，其中的阻燃机包括蜜白胺，蜜勒胺，双三聚氰胺焦磷酸，聚磷酸三聚氰胺以及它们的混合物，磷酸铵，二氢磷酸铵，一氢磷酸铵，次 磷酸铝，次磷酸锌，次磷酸钙，次磷酸镁，亚磷酸钠，苯基次磷酸和其金属盐，二烷基次磷酸和其盐，单烷基次磷酸和其盐，丙烯羧机次磷酸及其盐，苯基丙烯羧基机次磷酸及其盐，芳基丙烯羧基次磷酸及其盐，磷杂菲化合物(DOPO)及其盐，苯醌缩聚物。
具体实施方式
本发明的二烷基次膦酸-烷基亚磷酸金属复合盐，其制备方法和用途可以通过下面的实施案例进一步得到说明。但是本发明的权利范围不限于所列举的案例。
实施案例1：二乙基次膦酸钠的制备
将1490g(14mol)的一水次磷酸钠和35克浓硫酸，和7.5kg去离子水加入到一16升带夹套的搪瓷压力反应釜中进行溶解。在溶液加热到100度后，将乙烯通过减压阀导入反应釜，使乙烯压力在6巴下达到饱和。然后在反应釜持续搅拌下将300克水和16克(0.06mol)的过硫酸钾的水溶液以稳定的滴加速度在6小时内滴入反应釜，在此过程反应釜保持搅拌，乙烯压力恒定在6巴，温度维持在100-110℃之间。在滴加结束后继续反应1小时，然后放掉乙烯减压至常压，并把温度降低至常温。得到固含量为21.0％的透明水溶液产物9632克(得率为97.5％)。
实施案例2：乙基亚膦酸的制备
将1640g(20mol)的无水亚磷酸和7.5kg去离子水加入到一16升带夹套的搪瓷压力反应釜中进行溶解。在溶液加热到100℃后，将乙烯通过减压阀导入反应釜，使乙烯压力在6巴下达到饱和。然后在持续搅拌下将200克水和12.2克(0.045mol)的过硫酸钾的水溶液以稳定的滴加速度在6小时内滴入反应釜，在此过程反应釜保持搅拌，乙烯压力恒定在6巴，温度维持在100-110℃之间。在滴加结束后继续反应1小时，然后放掉乙烯减压至常压，并把温度降低至常温。得到固含量为22.3％的透明水溶液产物9742克(得率 为98.3％)。
实施案例3：二乙基次膦酸-乙基亚膦酸铝
将实施案例1所得到的二乙基次膦酸钠水溶液8430克(含12mol二乙基次膦酸钠)与1486克的实施案例2反应获得的水溶液(含3mol乙基亚磷酸)在反应釜中混合，在搅拌下加热至90℃并保持温度，然后在搅拌下将3875克含46％重量百分比的14水硫酸铝水溶液(含6.01mol铝)在一小时内以稳定速度滴入反应釜。将得到的沉淀物过滤，用热水反复洗涤，最后在130℃下进行真空干燥，得到1897克产物(得率为97.9％)。
实施案例4：二乙基次膦酸-亚磷酸铝
将实施案例1所得到得二乙基次膦酸钠水溶液8430克(含12mol二乙基次膦酸钠)与533克46％的亚磷酸水溶液(含3mol亚磷酸)在反应釜中混合，在搅拌下加热至90℃并保持温度，然后在搅拌下将3875克含46％重量百分比的14水硫酸铝水溶液(含6.01mol铝)在一小时内以稳定速度滴入反应釜。将得到的沉淀物过滤，用热水反复洗涤，最后在130℃下进行真空干燥，得到1781克产物(得率为96.0％)。
实施案例5：二乙基次膦酸-乙基亚磷铝
将1274g的一水次磷酸钠(12mol),648g的五水亚磷酸钠(3mol)，和35克浓硫酸，和7.5kg水加入到一16升带夹套的搪瓷压力反应釜中进行溶解。在溶液加热到100度后，将乙烯通过减压阀导入反应釜，使乙烯压力在6巴下达到饱和。然后在反应釜持续搅拌下将300克水和16克(0.065mol)的过硫酸钾的水溶液以稳定的滴加速度在6小时内滴入反应釜，在此过程反应釜保持搅拌，乙烯压力恒定在6巴，温度维持在100-110℃之间。在滴加结束后继续反应1小时，然后放掉乙烯减压至常压，并把温度降低至90℃。然后在反应釜保持搅拌下将3857克含46％重量百分比的14水硫酸铝水溶液(含6.01mol铝)在一小时内以稳定速度滴入反应釜。将得到的沉淀物过滤， 用热水反复洗涤，最后在130℃下进行真空干燥，得到1882克产物(得率为97.0％)。
实施案例6-10，阻燃剂的应用
本发明实施案例采用的原料和来源如下：
(1)尼龙66树脂，EPR27，平顶山神马
(2)二乙基次膦酸铝，LFR-8003，江苏利思德新材料
(3)玻纤，ECS301UW，重庆国际复合材料有限公司
(4)MPP，Melapur 200，购自BASF
(5)硼酸锌，Firebrake ZB，购自US Borax
(6)抗氧剂，Irg 1098，购自BASF
塑料试样制备和测试
将阻燃剂与聚合物切片与表一的比例进行混合，然后用双螺杆造粒机在280℃的温度范围进行拉条，水冷，和切粒。将配好阻燃剂的聚合物切粒进行干燥后用单螺杆注塑机在285℃进行注射成型。
阻燃测试：根据UL94标准进行垂直阻燃测试。
熔融指数测试：阻燃剂对聚合物材料在加工过程的影响可以通过对注塑试样的熔融指数进行评估，材料的熔融指数越高，说明材料在加工过程分子分解的越严重，对材料的力学性能越不利。熔融指数的测试条件为275℃/2.16kg。
阻燃等级测试
样条的阻燃等级测试根据UL94燃烧标准进行，样品厚度为1.6mm，根据UL94的测试结果，阻燃材料可按下面情况分级：
V0：样条离火后10秒内燃烧火焰熄灭，没有熔滴。
V1：样条离火后30秒内燃烧火焰熄灭，熔滴未引燃下方的棉花球。
V2：样条离火后30秒内燃烧火焰熄灭，熔滴引燃下方的棉花球。
设备腐蚀指数测试：阻燃剂在加工过程对设备的腐蚀可以用腐蚀指数表示，腐蚀指数越高，说明材料在加工过程对设备的腐蚀越严重。设备腐蚀指数由安装在注塑机模头的一个带有12x15x3mm挤出口的模块组成，在一定温度下通过这个模块注塑25公斤模塑料后检测模口的重量损失。
实施案例的测试结果如表一所示。
表一
Figure PCTCN2020076237-appb-000002
从表一的结果可见，单独使用二乙基次膦酸铝的阻燃效率不高，实施案例6在同样添加20％的阻燃剂时只达到了V1的阻燃等级，通常二乙基次膦酸铝阻燃剂需要添加MPP(三聚氰胺多聚磷酸)作为协效剂以提高阻燃体系的阻燃效率，但从表一的结果也看到，实施案例7添加MPP后造成聚合物分子的显著分解，熔融指数大幅升高。同时对设备的腐蚀性也非常显著。
从表一的结果可以看到，本发明的实施案例7-9都能很好的改善了阻燃效率，同时大大降低了聚合物在加工过程的分解，也明显改善了加工过程材料对设备的腐蚀。

Claims (11)

  1. 一种二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其特征在于，其化学成分为如式(1)：
    Figure PCTCN2020076237-appb-100001
    其中R1，R2，R3相同或不同，为H，或直链或支链的C1-C8饱和烷基，或直链或支链C2-C8不饱和烯基或C6-C8芳基，或含有羧基，羟基，胺基，酯基，酰胺基，环氧基，或者卤代的有机基团，
    其中M为Ca，Mg，Sb，Sn，Ge，Ti，Zn，Fe，Zr，Ce，Al，Sr，Mn金属阳离子和/或质子化的氮碱，其中
    m为金属阳离子的离子价位数，
    x为0至(m-0.01)的任意数，
    y为0.005至(m/2)的任意数，
    其中金属阳离子M的阳离子价位总数与二烷基次膦酸-烷基亚膦酸阴离子价位总数相等。
  2. 如权利要求1所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其特征在于，其中的R1，R2，R3选自氢，甲基，乙基，丙基，丁基，苯乙烯基。
  3. 如权利要求1或2所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其特征在于，其中M为Ca，Mg，Sn，Zn，Fe，Ti，Al金属阳离子。
  4. 如权利要求1至3中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其特征在于，
    其中
    x为1至(m-0.01)的任意数，
    y为0.005至(m-1)/2的任意数。
  5. 如权利要求1至4中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其特征在于，其中
    x为1.6至(m-0.01)的任意数，
    y为0.015至(m/2-0.8)的任意数。
  6. 如权利要求1至5中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其特征在于，其具有0.1至1000μm的平均粒子尺寸，0.01至10g/L的在水中的溶解度，80至800g/L的堆密度和0.1至5％的残留水分。
  7. 一种制备如权利要求1至6中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物的制备方法，其特征在于：将含有烷基亚磷酸或其碱金属盐和二烷基次膦酸或其碱金属盐混合物的水溶液与金属化合物进行复分解反应得到相应二烷基次膦酸-烷基亚磷酸金属复合盐，其中，这里烷基亚磷酸或其碱金属盐包括氢基亚磷酸和其碱金属盐，金属化合物为金属氢氧化物，有机酸和无机酸的金属盐。
  8. 一种如权利要求1至6中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物的用途，其特征在于，用于清漆和发泡涂料的阻燃剂，用于木材和其它含纤维素产品的阻燃剂，用于聚合物的反应性和/或非反应性阻燃剂，用于制备阻燃热塑性或热固性聚合物模塑材料，用于制备阻燃聚合物成型体和/或用于通过聚酯熔融纺丝的阻燃剂和纤维纺织物和混合织物配备阻燃性，以及作为阻燃剂混合物和阻燃剂中的协效剂。
  9. 一种阻燃热塑性或热固性聚合物模塑材料、聚合物成型体、聚合物膜、聚合物丝和聚合物纤维，其特征在于，其包含0.1至45重量％的含有如权利要求1-6中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物的阻燃剂组合物、55至99.9重量％的热塑性或热固性聚合物或其 混合物、0至30重量％的添加剂和0至55重量％的填料或者增强材料，其中各组分之和为100重量％。
  10. 如权利要求9所述阻燃剂组合物，其特征在于，该阻燃剂组合物含有50至99.9重量％的如权利要求1-6中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，和0.1至50重量％的其他阻燃剂和或协效剂，其中的阻燃协效剂为：三聚氰胺的缩合产物和/或三聚氰胺与磷酸的反应产物和/或三聚氰胺与聚磷酸或其混合物的反应产物和/或三聚氰胺与尿氰酸或其混合物的缩聚产物，式(NH 4) yH 3-yPO 4或者(NH 4PO 3) z的含氮磷酸盐，其中y等于1至3和z等于1至10,000；苯并胍胺、三(羟乙基)异氰脲酸酯、尿囊素、甘脲、三聚氰胺、氰尿酸三聚氰胺、双氰胺和/或胍；氧化镁、氧化钙、氧化铝、氧化锌、氧化锰、氧化锡、氢氧化铝、勃姆石、二水滑石、水铝钙石、氢氧化镁、氢氧化钙、氢氧化锌、氧化锡水合物、氢氧化锰、硼酸锌、碱性硅酸锌和/或锡酸锌、磷酸锌。
  11. 如权利要求9所述阻燃剂组合物，其特征在于，该阻燃剂组合物含有50至99.9重量％的阻燃剂，和0.1至50重量％如权利要求1-6中任一项所述的二烷基次膦酸-烷基亚膦酸金属复合盐和/或其混合物，其中的阻燃剂为：磷酸酯，次磷酸铝、次磷酸锌、次磷酸钙、亚磷酸钠、单苯基次膦酸及其盐、二烷基次膦酸及其盐与单烷基次膦酸及其盐的混合物、2-羧乙基烷基次膦酸及其盐、2-羧乙基甲基次膦酸及其盐、2-羧乙基芳基次膦酸及其盐、2-羧乙基苯基次膦酸及其盐、氧杂-10-磷杂菲(DOPO)及其盐和对苯醌上的加合物或者衣康酸及其盐，蜜白胺、蜜勒胺、蜜隆、二蜜胺焦磷酸盐、蜜胺聚磷酸盐、蜜白胺聚磷酸盐、蜜隆聚磷酸盐和/或蜜勒胺聚磷酸盐和/或它们的混合聚盐和/或为磷酸氢铵、磷酸二氢铵和/或聚磷酸铵。
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