WO2023168791A1 - 无卤阻燃剂组合物及其应用 - Google Patents

无卤阻燃剂组合物及其应用 Download PDF

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WO2023168791A1
WO2023168791A1 PCT/CN2022/087308 CN2022087308W WO2023168791A1 WO 2023168791 A1 WO2023168791 A1 WO 2023168791A1 CN 2022087308 W CN2022087308 W CN 2022087308W WO 2023168791 A1 WO2023168791 A1 WO 2023168791A1
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aluminum
flame retardant
halogen
free flame
retardant composition
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French (fr)
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李金忠
雷华
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江苏利思德新材料有限公司
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    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08K5/34—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K2003/387—Borates
    • 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

Definitions

  • the invention relates to the field of new materials, specifically to a halogen-free flame retardant composition and its application.
  • the core component of the halogen-free flame retardant composition is a phosphorus-containing aluminum salt composite based on aluminum ethylbutylphosphinate.
  • the body (referred to as the phosphorus-containing aluminum salt composite or composite, the same below) is particularly suitable for halogen-free flame retardant glass fiber reinforced engineering plastics, with the purpose of obtaining halogen-free flame retardant materials with low shrinkage.
  • Glass fiber reinforced engineering plastics (such as various nylons, polyesters, etc.) are widely used in the field of electronic and electrical appliances due to their good rigidity, impact resistance, low warpage, good surface appearance and other performance characteristics. Applications in these fields put forward flame retardant requirements for materials, and most engineering plastics are flammable materials. After compounding with glass fiber, the glass fiber reinforced engineering plastics are more likely to burn due to the wick effect of the glass fiber. Therefore, when glass fiber reinforced engineering plastics are used in these fields, they need to solve the problem of flame retardancy, and the existence of the wick effect makes it more difficult to flame retardant.
  • halogen flame retardant systems usually use brominated flame retardants in conjunction with antimony trioxide.
  • brominated flame retardants will produce harmful substances such as thick smoke and hydrogen bromide when burned. Can cause suffocation in the human body. Therefore, the development of safe, environmentally friendly, halogen-free flame retardant systems for glass fiber reinforced engineering plastics has become a research hotspot. In recent years, new halogen-free flame retardants or flame retardant systems for glass fiber reinforced engineering plastics have emerged.
  • the mainstream of halogen-free flame retardants used in glass fiber reinforced engineering plastics is a compound system based on aluminum diethyl phosphinate, which includes the synergy of aluminum diethyl phosphinate and nitrogen-containing compounds, such as diethyl phosphinate.
  • Aluminum diethyl phosphinate compounded with melamine polyphosphate (MPP) system and nitrogen-free aluminum diethylphosphinate and aluminum phosphite compound system. These systems have high flame retardancy, high temperature resistance and no color problems, and are currently used in a large number of applications.
  • the compound system based on diethyl aluminum phosphinate has an obvious crystalline transformation process at around 179°C, and during the molding process, this process will be experienced during the cooling and shaping stage. There is a large volume shrinkage during crystal transformation, which will cause large size differences in molded products. In some application fields that require high dimensional stability, a lower molding shrinkage rate is required, which will not meet the application requirements. If there is no crystalline transformation of aluminum diethylphosphinate, the molding shrinkage of the material will be reduced and the dimensional stability of the molded products will be improved.
  • the present invention proposes a flame retardant composition (also known as (Referred to as a "flame-retardant compound system”), the phosphorus-containing aluminum salt complex has an adjustable crystal transformation process, a lower crystal transformation temperature and lower energy absorption during the crystal transformation process. Under certain conditions There is no crystal form transformation process; in addition, when it is compounded with aluminum diethylphosphinate, it can significantly affect the crystal form transformation of aluminum diethylphosphinate, which can lower the crystal form transformation temperature and reduce the crystal form transformation process. Energy absorption, and under certain conditions, the crystal form transformation of aluminum diethylphosphinate will disappear.
  • the main purpose of the present invention is to provide a new halogen-free flame retardant compound system that can be applied to glass fiber reinforced engineering plastics to overcome the shortcomings of the existing flame retardant system.
  • the newly invented flame retardant system enables the material to have lower molding shrinkage while maintaining high flame retardancy.
  • the present invention relates to the development of a new halogen-free flame retardant compound system that can be applied to glass fiber reinforced engineering plastics. It uses a phosphorus-containing aluminum salt complex based on aluminum ethylbutylphosphinate as the core component, partially or completely replacing the two Aluminum ethylphosphinate synergizes with aluminum phosphite and/or its derivatives, and/or other nitrogen-containing compounds, zinc salt heat-stable compounds and other compounds to form a synergistic compound flame retardant with lower crystalline transformation effects. system to solve the negative impact caused by the obvious crystalline transformation during the processing of the existing flame retardant system based on diethyl aluminum phosphinate. This new flame retardant system can be well adapted to glass fiber reinforced engineering plastics, resulting in halogen-free flame retardant materials with lower molding shrinkage.
  • a halogen-free flame retardant composition in terms of mass percentage, the composition includes:
  • the phosphorus-containing aluminum salt complex based on aluminum ethylbutylphosphinate contains:
  • R 1 and R 2 are independently selected from H or C1-C6 alkyl groups, and when either R 1 or R 2 is an ethyl group, the other is not a butyl group;
  • R 3 is H or a C1-C6 alkyl group.
  • the present invention aims to solve the defects existing in the existing halogen-free flame retardant system based on aluminum diethylphosphinate that are widely used in glass fiber reinforced engineering plastics due to the crystal form transformation of aluminum diethylphosphinate.
  • the invention People have conducted extensive and in-depth research.
  • the above-mentioned phosphorus-containing aluminum salt complex based on ethyl butyl aluminum phosphinate has a different crystal form transformation from aluminum diethyl phosphinate. Even under certain conditions, such as the ethyl butyl aluminum salt complex in the complex When the molar content of aluminum phosphinate is not less than 30%, the crystalline transformation in the complex will disappear. Moreover, the phosphorus-containing aluminum salt complex can adjust the crystal form transformation of aluminum diethyl phosphinate, reduce the crystal form transformation temperature of aluminum diethyl phosphinate and the energy absorption during crystal form transformation, and even make diethyl phosphinate The crystalline transformation of aluminum phosphonate disappears.
  • the phosphorus-containing aluminum salt complex of the present invention is different from a single aluminum salt or a mixture of several aluminum salts. It exhibits different properties and is a compound with a new structure.
  • the phosphorus-containing aluminum salt complex based on aluminum ethylbutylphosphinate has the structure shown in the following formula (IV):
  • Formula (IV) represents a preferred complex formed between aluminum ethylbutylphosphinate and other phosphorus-containing aluminum salts, including aluminum diethylphosphinate, a type of aluminum ethylbutylphosphinate except ethylbutylphosphinate.
  • the phosphorus-containing aluminum salt complex of the present invention is formed of dialkyl aluminum phosphinate, a monoalkyl aluminum phosphinate, an inorganic aluminum phosphite, and the like other than aluminum acid and diethyl aluminum phosphinate.
  • Aluminum ethylbutylphosphinate can form an aluminum salt complex with one or more phosphorus-containing aluminum salts.
  • a is 0.2-0.99.
  • the invention also provides a preferred preparation method of the phosphorus-containing aluminum salt complex, which includes the steps:
  • the soluble salt is usually sodium salt or potassium salt
  • the aluminum-containing compound is preferably at least one of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, and aluminum oxide;
  • the end point of the washing is preferably when the conductivity of the washing water is less than 500 ⁇ s/cm.
  • step (1) the phosphorus-containing composite anion donor and the aluminum ion donor can be added in an equal molar ratio for complete reaction.
  • the strong acid includes concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, and concentrated phosphoric acid, and the amount added can be 2% to 5% of the mass of the phosphorus-containing composite anion donor.
  • the aluminum-containing compound When the aluminum-containing compound is insoluble in water, the aluminum-containing compound can be dispersed in water to form a suspended dispersion system. At this time, it reacts with the phosphorus-containing composite anion donor added in the form of an acid, and the presence of a high concentration of strong acid may not be required; When the aluminum compound is a water-soluble compound, it is recommended to react in the presence of a high concentration of strong acid. At this time, it can react with a phosphorus-containing complex anion donor added in the form of a salt.
  • the mass concentration of the aluminum-containing compound in the reaction system is preferably 15%-50%.
  • the reaction time can be 1-5 hours.
  • step (2)
  • the liquid phase pH can be controlled to be less than 4 to obtain a solid precipitate; the pH can be controlled by adding alkali or metal oxides;
  • the drying can use various ovens, drying rooms, dryers, etc., and the drying temperature can be 100-130°C.
  • High-temperature treatment is a key step in the preparation process.
  • the treatment process is related to the composition and proportion of the phosphorus-containing aluminum salt complex and the processing capacity.
  • the temperature setting of the high-temperature treatment is a key factor in the high-temperature treatment. Research has found that when the treatment temperature is lower than 180°C , the phosphorus-containing aluminum salt composite of the present application cannot be obtained, and the upper temperature limit of the high-temperature treatment is the decomposition temperature of the composite, which is usually lower than 450°C.
  • the high-temperature treatment process 0.5-10 hours to raise the temperature to 180-450°C for high-temperature treatment. , the time of high temperature treatment is 1-300min.
  • the high-temperature treatment process in step (2) can also be performed under an inert atmosphere (nitrogen atmosphere, rare gas atmosphere, etc.) or vacuum conditions.
  • the obtained phosphorus-containing aluminum salt composite can be pulverized to a required particle size as needed.
  • the phosphorus-containing aluminum salt complex of the present invention is characterized by DSC (differential scanning calorimetry). Taking the aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.3) complex with the molecular structure shown in Figure 1 as an example (the numbers indicate the molar ratio of the composite aluminum salt, the same below), the The DSC diagram is shown in Figure 2. It can be seen from the DSC chart that the aluminum ethylbutylphosphinate-aluminum diethylphosphinate complex has no crystalline transformation peak.
  • Figure 3 is a DSC chart of a mixture of aluminum ethyl butyl phosphinate and aluminum diethyl phosphinate (mixing molar ratio 0.7:0.3).
  • Figures 4 and 5 show aluminum ethyl butyl phosphinate and aluminum diethyl phosphinate respectively.
  • DSC chart of aluminum phosphinate From the results, it can be seen that the composite with the new structure shown in Figure 1 is prepared according to the preparation method of the present invention, which is different from the mixture of the two. In a mixture of the two, the DSC reflects the characteristics of the mixture.
  • the crystal transition temperature is the crystal transition temperature of aluminum diethylphosphinate.
  • the compound salt is not a mixture of the two, but a new structure.
  • aluminum diethylphosphinate has an obvious crystalline transformation
  • aluminum ethylbutylphosphinate (0.05)-diethylphosphinate
  • the aluminum ethyl phosphinate (0.95) complex has a lower crystal transition temperature and heat absorption (see Figure 6)
  • the aluminum ethyl butyl phosphinate (0.7)-aluminum diethyl phosphinate (0.3 ) complex DSC results show that there is no crystalline transformation.
  • These phosphorus-containing aluminum salt complexes can obviously overcome the negative effects caused by the crystal form transformation of aluminum diethylphosphinate and may replace aluminum diethylphosphinate.
  • the phosphorus-containing aluminum salt composite of the present invention under certain conditions, still has good flame retardancy when used in place of aluminum diethylphosphinate, including when used in conjunction with other amorphous systems. performance, while solving the problem of crystal form transformation of aluminum diethylphosphinate. Although there is no crystalline transformation of aluminum ethylbutylphosphinate, the phosphorus content of aluminum ethylbutylphosphinate (19.6%) is much lower than that of aluminum diethylphosphinate (23.8%), and the phosphorus content It is an important indicator for measuring phosphorus flame retardants, so it cannot completely replace aluminum diethylphosphinate.
  • the phosphorus-containing aluminum salt complex of the present invention is characterized by no crystalline transformation, or even in the presence of crystalline transformation, its crystalline transformation has lower endothermic characteristics and lower crystalline transformation temperature, and has a higher
  • the phosphorus content of the compound is synergistic, has good flame retardancy, has a high initial decomposition temperature, low water solubility, is resistant to migration and does not absorb moisture, and can be used as a flame retardant in nylon, PBT ( In engineering plastics such as polybutylene terephthalate), especially in glass fiber reinforced engineering plastics. In some application fields, in order to improve the flame retardant performance, it needs to be compounded with synergists to achieve good flame retardant effects.
  • the aluminum phosphite and its derivatives include aluminum phosphite, aluminum hydrogen phosphite, aluminum pyrophosphate and composites based on aluminum phosphite.
  • nitrogen-containing compounds can also be added as synergistic components to meet the flame retardant requirements of certain application fields. These nitrogen-containing compounds have no Crystalline transformation.
  • Figure 8 shows the DSC results of MPP without crystalline transformation.
  • the nitrogen-containing compounds include MPP (melamine polyphosphate), MCA (melamine cyanurate), etc.
  • Aluminum diethylphosphinate has an obvious crystal form transition, but the phosphorus-containing aluminum salt complex can adjust its crystal form transition, which can reduce the energy absorption and crystal form transition temperature during crystal form transition, and even make diethylphosphinic acid
  • the disappearance of the crystal form transformation of aluminum can also reduce the impact of the crystal form transformation and reduce the molding shrinkage of the material.
  • Figures 9 and 10 respectively show different proportions of phosphorus-containing composite aluminum salts (aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.3) complex) and aluminum diethylphosphinate. The final DSC results.
  • Zinc salt heat-stable compounds that can withstand high temperatures and do not precipitate can be introduced into the synergistic system formed by the phosphorus-containing aluminum salt complex, aluminum phosphite and its derivatives, which can further improve corrosion resistance and flame retardancy. There is no problem of precipitation.
  • These zinc salt thermally stable compounds have no crystalline transformation.
  • Figure 11 shows the DSC results of zinc borate without crystalline transformation.
  • Zinc salt heat-stable compounds include zinc borate and zinc stannate.
  • Zinc salt heat-stable compounds that do not contain crystal water have a high decomposition temperature, low water solubility, and do not migrate or precipitate.
  • the average particle size D50 of the phosphorus-containing aluminum salt complex based on aluminum ethylbutylphosphinate satisfies 5 ⁇ m ⁇ D50 ⁇ 50 ⁇ m;
  • the aluminum phosphite and/or its derivatives have no crystalline transformation characteristics, and the average particle size D50 satisfies 5 ⁇ m ⁇ D50 ⁇ 50 ⁇ m;
  • the average particle size D50 of the aluminum diethylphosphinate satisfies 5 ⁇ m ⁇ D50 ⁇ 50 ⁇ m;
  • the nitrogen-containing compound has amorphous transformation characteristics, including at least one of MPP, MCA, triazine compounds, etc., and the average particle size D50 satisfies 5 ⁇ m ⁇ D50 ⁇ 50 ⁇ m;
  • the amorphous transformation characteristics of the zinc salt thermally stable compound include at least one of zinc borate, zinc oxide, zinc stannate, etc., and the average particle size D50 satisfies 5 ⁇ m ⁇ D50 ⁇ 50 ⁇ m.
  • the mass percentage of the material is 0 to 10%.
  • the halogen-free flame retardant composition may also include at least one of the following components (A)-(C):
  • the invention also provides the application of the halogen-free flame retardant composition in the flame retardancy of glass fiber reinforced engineering plastics.
  • the glass fiber reinforced engineering plastic can be at least one of glass fiber reinforced nylon, polyester, POK (polyketone), etc. as the polymer matrix.
  • the halogen-free flame retardant composition is a functional additive that imparts flame retardant properties to glass fiber reinforced engineering plastics. It must meet relevant standard requirements, based on the total mass of the glass fiber reinforced engineering plastics being 100%.
  • the added amount of the halogen-free flame retardant composition is preferably 5% to 40%.
  • the flame retardant grade of the glass fiber reinforced engineering plastic reaches UL94V-0 and has low molding shrinkage characteristics.
  • the glass fiber reinforced engineering plastic can also be a thin-walled product, and can meet the flame retardant standard of UL94V-0 as thin as 0.4mm.
  • the flame-retardant system needs to be evenly dispersed in the material.
  • a twin-screw extruder with a fiberglass port and a flame retardant powder feed port, various components are melted and blended in the extruder, and extruded and granulated.
  • the main advantages of the present invention include:
  • the multi-component synergistic compound flame retardant system based on the phosphorus-containing aluminum salt complex provided by the present invention overcomes the defects of the existing flame retardant system and can be used as a halogen-free flame retardant system for glass fiber reinforced engineering plastics, reducing the cost of The molding shrinkage of the material can be used to prepare new low-shrinkage halogen-free flame-retardant glass fiber reinforced special materials.
  • Figure 1 is the molecular structure of aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.3) complex;
  • Figure 2 is a DSC chart of the aluminum ethylbutylphosphinate-aluminum diethylphosphinate complex shown in Figure 1;
  • Figure 3 is a DSC chart of a mixture of aluminum ethylbutylphosphinate and aluminum diethylphosphinate (molar ratio 0.7:0.3);
  • Figure 4 is a DSC chart of aluminum ethylbutylphosphinate
  • Figure 5 is a DSC chart of aluminum diethylphosphinate
  • Figure 6 is a DSC chart of aluminum ethylbutylphosphinate (0.05)-aluminum diethylphosphinate (0.95) complex;
  • Figure 7 is a DSC chart of amorphous aluminum phosphite
  • Figure 8 is the DSC chart of MPP without crystalline transformation
  • Figure 9 is a DSC chart of aluminum diethylphosphinate after adding 8% (based on the total mass of the phosphorus-containing aluminum salt complex and aluminum diethylphosphinate being 100%) of the phosphorus-containing aluminum salt complex;
  • Figure 10 is a DSC chart of aluminum diethylphosphinate after adding 30% (based on the total mass of the phosphorus-containing aluminum salt complex and aluminum diethylphosphinate being 100%) of the phosphorus-containing aluminum salt complex;
  • Figure 11 is a DSC chart of zinc borate without crystalline transformation.
  • the preparation process is: Dissolve 120.4g (0.7mol) sodium ethylbutylphosphinate and 43.2g (0.3mol) sodium diethylphosphinate in 381.7g of water in a 2L reaction kettle, stir thoroughly and dissolve. A mixed solution of sodium ethylbutylphosphinate and sodium diethylphosphinate was obtained. Dissolve 57g of aluminum sulfate in 133g of water in a 500mL beaker, then add 4.0g of concentrated sulfuric acid with a concentration of 98wt% to the aluminum sulfate solution, mix thoroughly, and transfer to a dropping funnel.
  • Complex-3 Aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.2)-aluminum ethylhexylphosphinate (0.1) complex;
  • Complex-4 Aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.2)-aluminum phosphite (0.1) complex;
  • Complex-6 Aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.15)-aluminum ethylhexylphosphinate (0.1)-aluminum phosphinate (0.05) complex;
  • Complex-7 Aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.15)-aluminum ethylhexylphosphinate (0.1)-aluminum ethylphosphinate (0.05) complex ;
  • Complex-8 Aluminum ethylbutylphosphinate (0.7)-aluminum diethylphosphinate (0.15)-aluminum ethylphosphinate (0.1)-aluminum phosphinate (0.05) complex;
  • the compound flame retardant system is used in glass fiber reinforced nylon. Following the following steps and test methods to examine the performance of the flame retardant.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-1, aluminum phosphite, and MPP, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-1, aluminum phosphite, MPP and zinc borate, keeping the total amount of the flame retardant system unchanged.
  • Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-1, aluminum diethylphosphinate and aluminum phosphite, keeping the total amount of the flame retardant system unchanged.
  • Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • Example 1 The implementation process is the same as Example 1, except that the flame retardant system only uses a single component of the phosphorus-containing aluminum salt complex-1. Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • the implementation process is the same as Example 1, except that the flame retardant system uses aluminum diethylphosphinate and aluminum phosphite compound system. Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • Example 1 The implementation process is the same as Example 1, except that the flame retardant system only uses aluminum diethylphosphinate as a single component. Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • the implementation process is the same as in Example 1, except that the flame retardant system uses a mixture of aluminum ethylbutylphosphinate and aluminum diethylphosphinate in the same proportion to replace Complex-1.
  • Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • the implementation process is the same as Example 1, except that the flame retardant system uses aluminum ethyl butyl phosphinate and aluminum phosphite compound system. Other materials and proportions are shown in Table 1, and the obtained material results are shown in Table 1.
  • test conditions for each performance index in Table 1, Table 2, and Table 3 are as follows:
  • DSC test method for powder performance of flame retardant system nitrogen atmosphere; heating rate: 10°C/min; temperature range: room temperature -300°C.
  • V-0 Each ignition does not exceed 10 seconds of afterburning. A total of 5 samples are ignited. Each sample is ignited twice. The sum of the afterburning times of 10 ignitions for the 5 samples is not greater than 50s. There is no burning or dripping. The sample is not completely burned out, and the sample does not smolder for more than 30 seconds after the ignition is completed;
  • V-1 Each ignition does not exceed 30 seconds of afterburning. A total of 5 samples are ignited. Each sample is ignited twice. The sum of the afterburning times of 10 ignitions for the 5 samples is not greater than 250s. There is no burning or dripping. The sample is not completely burned out, and the sample does not smolder for more than 60 seconds after the ignition is completed;
  • V-2 Ignite cotton by burning and dripping, other standards are the same as V-1
  • V-0 the test here only focuses on whether V-0 is reached. If it is reached, it is recorded as PASS, if it is not reached, it is recorded as FAIL.
  • the flame retardant test is related to thickness. The thinnest sample thickness is examined here, and the sample thickness is 0.4mm.
  • the material using a phosphorus-containing aluminum salt composite has a lower molding shrinkage than aluminum diethylphosphinate, and also has a lower molding shrinkage than aluminum ethylbutylphosphinate and aluminum diethylphosphinate in the same proportion. Mixture is low.
  • the combination of phosphorus-containing composite aluminum salt and synergist has higher flame retardancy and lower molding shrinkage.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-3, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-4, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-5, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-6, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-7, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • the implementation process is the same as in Example 1.
  • the flame retardant system is phosphorus-containing aluminum salt complex-8, and the total amount of the flame retardant system remains unchanged.
  • Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • Example 2 The implementation process is the same as Example 1, the flame retardant system is phosphorus-containing aluminum salt complex-9, and the total amount of the flame retardant system remains unchanged. Other materials and proportions are shown in Table 2, and the obtained material results are shown in Table 2.
  • Example 2 The implementation process is the same as in Example 1. A small amount of aluminum ethylbutylphosphinate is added to the flame retardant system to keep the total amount of the flame retardant system unchanged. Other materials and proportions are shown in Table 3, and the obtained material results are shown in Table 3.
  • Example 2 The implementation process is the same as in Example 1. A small amount of aluminum ethylphosphinate is added to the flame retardant system to keep the total amount of the flame retardant system unchanged. Other materials and proportions are shown in Table 3, and the obtained material results are shown in Table 3.
  • Example 2 The implementation process is the same as in Example 1. A small amount of aluminum phosphate is added to the flame retardant system to keep the total amount of the flame retardant system unchanged. Other materials and proportions are shown in Table 3, and the obtained material results are shown in Table 3.

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Abstract

一种无卤阻燃剂组合物及其在玻纤增强工程塑料阻燃中的应用。以质量百分比计，该无卤阻燃剂组合物组成包括：基于乙基丁基次膦酸铝的含磷铝盐复合体1％～99％，亚磷酸铝和/或其衍生物1％～99％，二乙基次膦酸铝0～80％，含氮化合物0～40％，锌盐热稳定化合物0～20％。该无卤阻燃剂组合物应用于玻纤增强工程塑料阻燃，具有低成型收缩特点，利用该无卤阻燃剂组合物所制备的无卤阻燃玻纤增强工程塑料，可达到UL94V-0的阻燃标准。

Description

无卤阻燃剂组合物及其应用 技术领域
本发明涉及新材料领域，具体涉及一种无卤阻燃剂组合物及其应用，该无卤阻燃剂组合物的核心组分为基于乙基丁基次膦酸铝的含磷铝盐复合体(简称含磷铝盐复合体或复合体，以下同)，特别适用于玻纤增强工程塑料的无卤阻燃，目的是得到具有低收缩率的无卤阻燃材料。
背景技术
玻纤增强工程塑料(如各种尼龙、聚酯等)因具有良好的刚性和抗冲击性、低翘曲性、良好的表面外观等性能特点而被广泛应用于电子电器领域。在这些领域的应用，对材料提出了阻燃的要求，而大多工程塑料是易燃材料，在与玻纤复合后，由于玻纤的灯芯效应，使得玻纤增强工程塑料更容易燃烧。因此玻纤增强工程塑料在这些领域应用时，需要解决阻燃的问题，而且灯芯效应的存在使得其阻燃难度更大。
对于玻纤增强工程塑料的阻燃，包括了两类基本的阻燃体系：卤系阻燃体系和非卤阻燃体系。卤系阻燃体系通常是含溴阻燃剂协同三氧化二锑，大量研究表明，添加有溴系阻燃剂的玻纤增强工程塑料在燃烧时会产生浓烟和溴化氢等有害物质，会引起人体窒息。因此，为玻纤增强工程塑料开发安全、环保、无卤阻燃体系成为研究的热点，近年来出现了新型的应用于玻纤增强工程塑料的无卤阻燃剂或阻燃体系。
目前，应用于玻纤增强工程塑料的无卤阻燃剂主流是基于二乙基次膦酸铝的复配体系，包括了二乙基次膦酸铝和含氮化合物的协同，例如，二乙基次膦酸铝复配三聚氰氨聚磷酸盐(MPP)体系，以及不含氮的二乙基次膦酸铝与亚磷酸铝的复配体系。这些体系具有高阻燃性、耐高温以及无颜色困扰等问题，目前也得到了大量的应用。但基于二乙基次膦酸铝的复配体系，由于二乙基次膦酸铝在179℃左右有明显的晶型转变过程，而在成型过程中，降温定型阶段会经历该过程，由于在晶型转变时存在较大的体积收缩，会引起成型制品大的尺寸差异，在一些对尺寸稳定性要求较高 的应用领域，需要更低的成型收缩率，此时将无法满足应用的要求。如果二乙基次膦酸铝不存在晶型转变，材料的成型收缩率会降低，成型制品的尺寸稳定性能将会提高。因此，在这些应用中，希望二乙基次膦酸铝的晶型转变可以调整，改变晶型转变温度，降低晶型转变过程中的能量吸收或者不存在晶型转变过程，这样就可减少在应用过程中的负面作用。
为了解决二乙基次膦酸铝的晶型转变的负面影响，有必要开发新的阻燃体系。针对该问题，主要有两种方案：(1)使用可替代二乙基次膦酸铝的组分，在保持阻燃性能的同时，没有晶型转变过程的存在，或者晶型转变过程能量的吸收更低；(2)加入可调控二乙基次膦酸铝的晶型转变的组分，改变二乙基次膦酸铝的晶型转变温度，降低晶型转变过程能量的吸收，甚至使其晶型转变消失。而关于这两种解决问题的方案，未见相关报道。
发明内容
针对上述技术问题以及本领域存在的不足之处，本发明提出了一种以基于乙基丁基次膦酸铝的含磷铝盐复合体为核心组分的阻燃剂组合物(亦可称为“阻燃复配体系”)，该含磷铝盐复合体具有可调的晶型转变过程，有较低的晶型转变温度和晶型转变过程中更低的能量吸收，在一定条件下不存在晶型转变过程；此外，当其和二乙基次膦酸铝复配时，可以明显影响二乙基次膦酸铝的晶型转变，可降低晶型转变温度，降低晶型转变过程能量的吸收，并在一定条件下，二乙基次膦酸铝的晶型转变会消失。而且在阻燃性能上，含磷铝盐复合体取代二乙基次膦酸铝或与二乙基次膦酸铝复配使用时，整个复配体系的阻燃性能不受影响，这样可以满足低收缩要求的特殊领域的应用。
本发明的主要目的是提供一种可应用于玻纤增强工程塑料的新型无卤阻燃复配体系，克服现有阻燃体系的缺陷，新发明的该种阻燃体系使得材料具有更低的成型收缩率，同时保持了高阻燃性。
本发明涉及可应用于玻纤增强工程塑料的新型无卤阻燃复配体系的开发，以基于乙基丁基次膦酸铝的含磷铝盐复合体为核心组分，部分或全部替代二乙基次膦酸铝，通过与亚磷酸铝和/或其衍生物，和/或其它含氮化合物、锌盐热稳定化合物等化合物协同，形成具有更低晶型转变影响的协同复配阻燃体系，解决现有基于二乙基次膦酸铝阻燃体系加工过程明显 晶型转变带来的负面影响。该新型阻燃体系可以很好地适应玻纤增强工程塑料，得到具有更低成型收缩率的无卤阻燃材料。
具体技术方案如下：
一种无卤阻燃剂组合物，以质量百分比计，其组成包括：
Figure PCTCN2022087308-appb-000001
所述基于乙基丁基次膦酸铝的含磷铝盐复合体包含有：
结构式(I)的含磷结构，以及
结构式(II)和/或结构式(III)所指代的一种或多种含磷结构；
Figure PCTCN2022087308-appb-000002
结构式(II)中，R 1、R 2分别独立选自H或C1-C6的烷基，且当R 1、R 2中任一个为乙基时，另一个不为丁基；
结构式(III)中，R 3为H或C1-C6的烷基。
本发明是以解决现有广泛应用于玻纤增强工程塑料中的基于二乙基次膦酸铝的无卤阻燃体系中由于二乙基次膦酸铝晶型转变存在的缺陷为目的，发明人进行了广泛而深入的研究。
经过研究发现，上述基于乙基丁基次膦酸铝的含磷铝盐复合体有着与二乙基次膦酸铝不同的晶型转变，甚至在一定条件下，如复合体中乙基丁基次膦酸铝摩尔含量不小于30％时，复合体中的晶型转变会消失。而且该含磷铝盐复合体可以调整二乙基次膦酸铝的晶型转变，降低二乙基次膦酸铝的晶型转变温度和晶型转变时的能量吸收，甚至使得二乙基次膦酸铝的晶型转变消失。
本发明的含磷铝盐复合体不同于单一铝盐或几种铝盐的混合物，表现出了不同的性质，是一种具有新的结构的化合物。
在一优选例中，所述基于乙基丁基次膦酸铝的含磷铝盐复合体具有如下式(IV)所示结构：
Figure PCTCN2022087308-appb-000003
式(IV)中，a、b、c、d、e均为摩尔比，a为0.01-0.99，b、c、d、e为0-0.99且不同时为0，a+b+c+d+e＝1，R 1、R 2分别独立选自C1-C6的烷基，且当R 1、R 2中任一个为乙基时，另一个不为乙基和丁基，R 3为C1-C6的烷基。
式(IV)表示了乙基丁基次膦酸铝与其它含磷铝盐形成的优选的复合体，其它含磷铝盐包括二乙基次膦酸铝、一种除乙基丁基次膦酸铝和二乙基次膦酸铝外的二烷基次膦酸铝、一种单烷基亚膦酸铝、一种无机的亚磷酸铝等形成的本发明的含磷铝盐复合体。乙基丁基次膦酸铝可以与其中的一种或多种含磷铝盐形成铝盐复合体。
进一步优选，式(IV)中，a越大，复合体的晶型转变调控能力越大，优选a为0.2-0.99。
本发明还提供了所述的含磷铝盐复合体的一种优选制备方法，包括步骤：
(1)将包含有结构式(I)的阴离子部分的乙基丁基次膦酸和/或可溶性乙基丁基次膦酸盐与其它参与复合的包含有结构式(II)和/或结构式(III)的阴离子部分的酸和/或可溶性盐(含磷复合阴离子供体)溶于水(水中可以加入少量强酸或不加入强酸)中，再加入含铝化合物(铝离子供体)，在80-90℃下反应；
(2)反应结束后，固液分离取固体洗涤、干燥，然后在180-450℃下高温处理得到所述的含磷铝盐复合体。
上述制备方法中：
所述的可溶性盐通常是钠盐或钾盐；
所述含铝化合物优选为硫酸铝、硝酸铝、氯化铝、氢氧化铝、氧化铝中的至少一种；
所述洗涤的终点优选为洗涤出水的电导率小于500μs/cm。
步骤(1)中，含磷复合阴离子供体、铝离子供体可按完全反应等摩尔比加入。
步骤(1)中，所述强酸包括浓硫酸、浓硝酸、浓盐酸、浓磷酸，添加量可以为含磷复合阴离子供体质量的2％-5％。
所述含铝化合物不溶于水时，可以把含铝化合物分散于水中形成悬浮分散体系，此时其与以酸形式添加的含磷复合阴离子供体反应，可以不需要高浓度的强酸存在；含铝化合物为水溶性化合物时，建议有高浓度的强酸存在的条件下反应，此时其可以与以盐形式添加的含磷复合阴离子供体反应。
含铝化合物在反应体系中的质量浓度优选为15％-50％。
步骤(1)中，反应时间可以是1-5小时。
步骤(2)中：
反应结束可通过控制液相pH小于4，得到固体沉淀物；pH的控制可以通过加入碱或金属氧化物等实现；
所述干燥可以采用各种烘箱、烘房、干燥器等，干燥温度可以是100-130℃。高温处理是制备工艺的关键步骤，处理工艺和含磷铝盐复合体的组成及比例、处理量有关，高温处理的温度设置是高温处理的关键因素，研究发现，当处理温度低于180℃时，不能得到本申请的含磷铝盐复合体，而高温处理的温度上限为复合体的分解温度，通常低于450℃，高温处理的工艺：0.5-10小时升温至180-450℃进行高温处理，高温处理的时间为1-300min。
步骤(2)的高温处理过程也可以在惰性氛围(氮气气氛、稀有气体气氛等)或真空条件下进行。
在步骤(2)后，可以根据需要将得到的含磷铝盐复合体粉碎至所需粒径。
研究发现，要得到本发明的含磷铝盐复合体，制备方法中的两个步骤都必不可少，即不进行高温处理(包括处理温度低于180℃)或者只是几种含磷铝盐干混后高温热处理都不能得到本申请的含磷铝盐复合体。
对本发明的含磷铝盐复合体进行DSC(差示扫描量热)表征。以如图1所示分子结构的乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体(数字表示复合铝盐的摩尔比，下同)为例，其DSC图如图2所示。 从DSC图上可以看出，此乙基丁基次膦酸铝-二乙基次膦酸铝复合体没有晶型转变峰。图3是乙基丁基次膦酸铝和二乙基次膦酸铝混合物(混合摩尔比0.7:0.3)的DSC图，图4和图5分别为乙基丁基次膦酸铝和二乙基次膦酸铝的DSC图。从结果看，按照本发明制备方法制备得到的是图1所示的新结构的复合体，与两者的混合物是不同的。在两者的混合物中，其DSC体现了混合物特性，晶型转变温度是二乙基次膦酸铝的晶型转变温度，由于比例的降低，晶型转变的焓值降低了；而在复合体里，相同的比例下，二乙基次膦酸铝的特征晶型转变峰消失了。因此复合盐不是两者的混合物，而是一种新的结构。
从DSC结果看，二乙基次膦酸铝具有明显的晶型转变，而基于乙基丁基次膦酸根的含磷复合铝盐中，乙基丁基次膦酸铝(0.05)-二乙基次膦酸铝(0.95)复合体具有更低的晶型转变温度和吸热量(参见图6)，而乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体，DSC结果显示不存在晶型转变。这些含磷铝盐复合体，显然可以克服二乙基次膦酸铝晶型转变带来的负面影响，有可能取代二乙基次膦酸铝。
进一步的研究发现，本发明的含磷铝盐复合体，在一定条件下，在取代二乙基次膦酸铝进行应用时，包括和其它非结晶性体系协同应用时，仍然具有好的阻燃性能，同时解决了二乙基次膦酸铝晶型转变的问题。虽然乙基丁基次膦铝也不存在晶型转变，但由于乙基丁基次膦酸铝的磷含量(19.6％)远低于二乙基次膦酸铝(23.8％)，而磷含量是衡量磷系阻燃剂的重要指标，因此并不能完全取代二乙基次膦酸铝。
本发明的含磷铝盐复合体，其特征是无晶型转变，或即使有晶型转变存在下，其晶型转变具有较低吸热特征和更低的晶型转变温度，并具有较高的磷含量，参与复合的含磷铝盐具有相互协同性，阻燃性好，具有较高的初始分解温度，水溶性低，耐迁移不吸潮，可以作为阻燃剂应用于尼龙、PBT(聚对苯二甲酸丁二醇酯)等工程塑料中，特别是玻纤增强的工程塑料中。在有些应用领域，为了提高阻燃性能，还需要和协效剂复配，达到好的阻燃效果。
发明人通过研究发现，该含磷铝盐复合体，与亚磷酸铝及其衍生物协同，可以进一步提高其阻燃性能，具有良好的协同，这些亚磷酸铝及其衍生物应为无晶型转变，图7为一种亚磷酸铝的DSC结果。所述的亚磷酸 铝及其衍生物，包括亚磷酸铝、亚磷酸氢铝、焦亚磷酸铝及基于亚磷酸铝的复合物。
研究发现，在含磷铝盐复合体与亚磷酸铝及其衍生物形成的协同体系中，也可以加入含氮化合物作为协同组分，满足某些应用领域的阻燃要求，这些含氮化合物无晶型转变，图8为无晶型转变的MPP的DSC结果。所述的含氮化合物，包括了MPP(三聚氰胺聚磷酸盐)、MCA(三聚氰胺氰尿酸盐)等。
研究发现，在含磷铝盐复合体与亚磷酸铝及其衍生物形成的协同体系中，也可以加入二乙基次膦酸铝，特别是弥补当复合体中乙基丁基次膦酸铝含量过高导致的磷含量的下降，并产生协同作用，满足某些应用领域的阻燃要求。二乙基次膦酸铝存在明显的晶型转变，但含磷铝盐复合体能调节其晶型转变，可以降低晶型转变时的能量吸收和晶型转变温度，甚至使得二乙基次膦酸铝的晶型转变消失，同样可以降低晶型转变的影响，降低材料的成型收缩率。图9和图10分别为不同比例的含磷复合铝盐(乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体)和二乙基次膦酸铝混合后的DSC结果。
此外，还发现在含磷铝盐复合体与亚磷酸铝及其衍生物形成的协同体系中可引入少量耐高温不析出的锌盐热稳定化合物，能进一步提高耐腐蚀，并提高阻燃性，还不存在析出的问题，这些锌盐热稳定化合物无晶型转变，图11为无晶型转变的硼酸锌的DSC结果。锌盐热稳定化合物包括了硼酸锌和锡酸锌，不含结晶水的锌盐热稳定化合物具有高的分解温度，水溶性低，不迁移析出。
基于以上研究，本发明可进行以下技术方案的优选：
所述基于乙基丁基次膦酸铝的含磷铝盐复合体的平均粒径D50满足5μm＜D50＜50μm；
所述亚磷酸铝和/或其衍生物无晶型转变特征，平均粒径D50满足5μm＜D50＜50μm；
所述二乙基次膦酸铝的平均粒径D50满足5μm＜D50＜50μm；
所述含氮化合物无晶型转变特征，包括MPP、MCA、三嗪化合物等中的至少一种，平均粒径D50满足5μm＜D50＜50μm；
所述锌盐热稳定化合物无晶型转变特征，包括硼酸锌、氧化锌、锡酸 锌等中的至少一种，平均粒径D50满足5μm＜D50＜50μm，在所述无卤阻燃剂组合物中的质量百分占比为0～10％。
所述无卤阻燃剂组合物中还可包括以下组分(A)-(C)中的至少一种：
(A)乙基丁基次膦酸盐、丁基丁基次膦酸盐、乙基己基次膦酸盐、丁基己基次膦酸盐、己基己基次膦酸盐中的一种或几种非复合盐；
(B)烷基亚膦酸盐；
(C)硫酸盐、氯化物、磷酸盐、亚磷酸盐、次磷酸盐、硝酸盐、乙酸盐、铵盐、含铁化合物、含钙化合物、含镁化合物、含钛化合物、含钠化合物、含钾化合物中的一种或几种。
本发明还提供了所述的无卤阻燃剂组合物在玻纤增强工程塑料阻燃中的应用。
所述玻纤增强工程塑料可以玻纤增强尼龙、聚酯、POK(聚酮)等中的至少一种作为聚合物基体。
所述的无卤阻燃剂组合物，是赋予玻纤增强工程塑料阻燃性能的功能性助剂，要达到相关的标准要求，以所述玻纤增强工程塑料的总质量为100％计，所述无卤阻燃剂组合物的添加量优选为5％～40％，所述玻纤增强工程塑料的阻燃等级达UL94V-0，且具有低成型收缩特点。
所述玻纤增强工程塑料还可以是薄壁制品，并可达到薄至0.4mm厚度的UL94V-0的阻燃标准。
要制备无卤阻燃玻纤增强材料，还需把阻燃体系均匀分散于材料中。则通过带加玻纤口和阻燃剂粉体进料口的双螺杆挤出机，各种组分在挤出机中完成熔融共混，并挤出造粒。
本发明与现有技术相比，主要优点包括：
本发明所提供的基于含磷铝盐复合体的多组分协同复配阻燃体系，克服了现有阻燃体系的缺陷，可以用作玻纤增强工程塑料的无卤阻燃体系，降低了材料的成型收缩率，可以制备新型的低收缩无卤阻燃玻纤增强专用材料。
附图说明
图1为乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体分子 结构；
图2为图1所示乙基丁基次膦酸铝-二乙基次膦酸铝复合体DSC图；
图3为乙基丁基次膦酸铝和二乙基次膦酸铝混合物(摩尔比0.7:0.3)的DSC图；
图4为乙基丁基次膦酸铝DSC图；
图5为二乙基次膦酸铝DSC图；
图6为乙基丁基次膦酸铝(0.05)-二乙基次膦酸铝(0.95)复合体DSC图；
图7为无晶型转变的亚磷酸铝的DSC图；
图8为无晶型转变的MPP的DSC图；
图9为加入8％(以含磷铝盐复合体、二乙基次膦酸铝总质量为100％计)的含磷铝盐复合体的二乙基次膦酸铝DSC图；
图10为加入30％(以含磷铝盐复合体、二乙基次膦酸铝总质量为100％计)的含磷铝盐复合体的二乙基次膦酸铝DSC图；
图11为无晶型转变的硼酸锌的DSC图。
具体实施方式
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。
如图1所示分子结构的乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体的合成
制备过程为：在2L的反应釜中把120.4g(0.7mol)乙基丁基次膦酸钠和43.2g(0.3mol)二乙基次膦酸钠溶于381.7g的水，充分搅拌溶解，得到乙基丁基次膦酸钠和二乙基次膦酸钠混合溶液。在500mL的烧杯中把57g硫酸铝溶于133g水中，再在硫酸铝溶液中加入4.0g浓度为98wt％的浓硫酸充分搅拌混合均匀，转移到滴液漏斗中。加热反应釜，升温至90℃，开始滴加含硫酸的硫酸铝溶液，2小时滴加完成，保温继续反应1小时。趁热过滤，并多次洗涤沉淀物，直至洗涤出水电导率小于200μs/cm，停止洗涤。转移物料至烘箱，升温至120℃，干燥60min，固体物水分含量为0.1wt％，再以2℃/min的速度升温至180℃，保持60min，再以1℃/min 升温至320℃，保持30min，降温至常温，出料，得到乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体，记为复合体-1。把物料粉碎，平均粒径D50为42μm，得率为96.5％。通过DSC测试样品的晶型转变，测试结果如图2所示。
参照上述制备过程，改变原料的种类和投料摩尔比即可得到其它复合体。
以下各实施例、对比例所涉及的阻燃剂体系中：
复合体-1：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.3)复合体，DSC结果如图2所示；
复合体-2：乙基丁基次膦酸铝(0.05)-二乙基次膦酸铝(0.95)复合体，DSC结果如图6所示；
复合体-3：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.2)-乙基己基次膦酸铝(0.1)复合体；
复合体-4：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.2)-亚磷酸铝(0.1)复合体；
复合体-5：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.2)-乙基亚膦酸铝(0.1)复合体；
复合体-6：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.15)-乙基己基次膦酸铝(0.1)-亚磷酸铝(0.05)复合体；
复合体-7：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.15)-乙基己基次膦酸铝(0.1)-乙基亚膦酸铝(0.05)复合体；
复合体-8：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.15)-乙基亚膦酸铝(0.1)-亚磷酸铝(0.05)复合体；
复合体-9：乙基丁基次膦酸铝(0.7)-二乙基次膦酸铝(0.1)-乙基己基次膦酸铝(0.1)-乙基亚膦酸铝(0.05)-亚磷酸铝(0.05)复合体，记为复合体-9；
二乙基次膦酸铝的DSC结果如图5所示；
亚磷酸铝的DSC结果如图7所示；
MPP的DSC结果如图8所示；
硼酸锌的DSC结果如图11所示。
如无特殊说明，各实施例、对比例中的物料用量均为质量份。
实施例1
复配阻燃体系应用于玻纤增强尼龙中，按下列步骤及测试方法考察阻燃剂的性能。
1)无卤阻燃剂体系的混配
按表1的配比在高搅机中加复配阻燃剂体系各组分，启动高速搅拌，搅拌10min，完成无卤阻燃剂体系的混配，出料，DSC检测，待用。
2)材料的挤出造粒
把双螺杆挤出机各区温度设置在预定温度，待温度稳定20min后，从料斗中加入尼龙体系，玻纤通过加玻纤口加入，阻燃剂粉体通过粉体加料孔加料，启动主机和喂料机，完成材料的挤出造粒。造好粒的物料通过风送系统送入料仓，并烘干。
3)材料的应用与测试
把烘干好的物料在注塑机中注塑出各种测试标准所规定的标准试样，并进行相关材料性能的测试。
本实施例中各物料及配比见表1，所得到的材料测试结果见表1。
实施例2
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-1、亚磷酸铝、MPP，保持阻燃体系总量不变。其它物料及配比见表1，所得到的材料结果见表1。
实施例3
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-1、亚磷酸铝、MPP和硼酸锌，保持阻燃体系总量不变。其它物料及配比见表1，所得到的材料结果见表1。
实施例4
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-1、二乙基次膦酸铝和亚磷酸铝，保持阻燃体系总量不变。其它物料及配比见表1，所得到的材料结果见表1。
对比例1
实施过程与实施例1相同，除了阻燃体系只使用含磷铝盐复合体-1单组分外。其它物料及配比见表1，所得到的材料结果见表1。
对比例2
实施过程与实施例1相同，除了阻燃体系使用二乙基次膦酸铝和亚磷酸铝复配体系外。其它物料及配比见表1，所得到的材料结果见表1。
对比例3
实施过程与实施例1相同，除了阻燃体系只使用二乙基次膦酸铝单组分外。其它物料及配比见表1，所得到的材料结果见表1。
对比例4
实施过程与实施例1相同，除了阻燃体系使用同比例的乙基丁基次膦酸铝和二乙基次膦酸铝混合物替代复合体-1外。其它物料及配比见表1，所得到的材料结果见表1。
对比例5
实施过程与实施例1相同，除了阻燃体系使用乙基丁基次膦酸铝和亚磷酸铝复配体系外。其它物料及配比见表1，所得到的材料结果见表1。
表1、表2、表3中各性能指标测试条件如下：
1、阻燃剂体系粉体性能DSC测试方法：氮气氛围；升温速度：10℃/min；温度范围：室温-300℃。
2、材料阻燃性能
依据UL94测试标准测试(试片厚度0.4mm)。根据UL94阻燃性能分如下等级：
V-0：每次点火不超过10s的续燃，共点5根试样，每根试样点火两次，5根样条10次点火的续燃时间总和不大于50s，没有燃烧滴落，试样没有完全燃尽，点火结束之后无大于30s试样阴燃；
V-1：每次点火不超过30s的续燃，共点5根试样，每根试样点火两 次，5根试样10次点火的续燃时间总和不大于250s，没有燃烧滴落，试样没有完全燃尽，点火结束之后无大于60s试样阴燃；
V-2：通过燃烧滴落引燃棉花，其余标准同V-1
这里测试只关注是否达到V-0，如果达到记为PASS，没达到记为FAIL。
阻燃测试和厚度有关，这里考察最薄的试样厚度，试样厚度为0.4mm。
3、材料成型收缩率：依据ASTM D955-2008所规定的方法测试。
表1
Figure PCTCN2022087308-appb-000004
从结果看，材料使用含磷铝盐复合体比二乙基次膦酸铝具有更低的成型收缩率，也比使用同比例的乙基丁基次膦酸铝和二乙基次膦酸铝混合物低。针对PA66体系，含磷复合铝盐与协同剂复配具有更高的阻燃性，同时也得到了更低的成型收缩率。
实施例5
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-3，保持阻燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
实施例6
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-4，保持阻燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
实施例7
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-5，保持阻燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
实施例8
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-6，保持阻燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
实施例9
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-7，保持阻燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
实施例10
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-8，保持阻燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
实施例11
实施过程与实施例1相同，阻燃剂体系为含磷铝盐复合体-9，保持阻 燃体系总量不变。其它物料及配比见表2，所得到的材料结果见表2。
表2
Figure PCTCN2022087308-appb-000005
表2的结果表明，基于乙基丁基次膦酸铝的多元含磷铝盐复合体，与协同剂作用，应用于尼龙材料，同样具有低的成型收缩率和好的阻燃性能。
实施例12
实施过程与实施例1相同，阻燃剂体系中加入少量的乙基丁基次膦酸铝，保持阻燃体系总量不变。其它物料及配比见表3，所得到的材料结果见表3。
实施例13
实施过程与实施例1相同，阻燃剂体系中加入少量的乙基亚膦酸铝，保持阻燃体系总量不变。其它物料及配比见表3，所得到的材料结果见表3。
实施例14
实施过程与实施例1相同，阻燃剂体系中加入少量的磷酸铝，保持阻燃体系总量不变。其它物料及配比见表3，所得到的材料结果见表3。
表3
Figure PCTCN2022087308-appb-000006
表3结果表明，本申请的阻燃剂组份中，少量其它非复合盐的存在，不影响本申请的成型收缩率及阻燃作用。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种无卤阻燃剂组合物，其特征在于，以质量百分比计，其组成包括：
    Figure PCTCN2022087308-appb-100001
    所述基于乙基丁基次膦酸铝的含磷铝盐复合体包含有：
    结构式(I)的含磷结构，以及
    结构式(II)和/或结构式(III)所指代的一种或多种含磷结构；
    Figure PCTCN2022087308-appb-100002
    结构式(II)中，R 1、R 2分别独立选自H或C1-C6的烷基，且当R 1、R 2中任一个为乙基时，另一个不为丁基；
    结构式(III)中，R 3为H或C1-C6的烷基。
  2. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述基于乙基丁基次膦酸铝的含磷铝盐复合体具有如下式(IV)所示结构：
    Figure PCTCN2022087308-appb-100003
    式(IV)中，a、b、c、d、e均为摩尔比，a为0.01-0.99，b、c、d、e为0-0.99且不同时为0，a+b+c+d+e＝1，R 1、R 2分别独立选自C1-C6的烷基，且当R 1、R 2中任一个为乙基时，另一个不为乙基和丁基，R 3为C1-C6的烷基。
  3. 根据权利要求2所述的无卤阻燃剂组合物，其特征在于，式(IV) 中，a为0.2-0.99。
  4. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述基于乙基丁基次膦酸铝的含磷铝盐复合体的平均粒径D50满足5μm＜D50＜50μm。
  5. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述亚磷酸铝和/或其衍生物无晶型转变特征，包括亚磷酸铝、亚磷酸氢铝、焦亚磷酸铝及基于亚磷酸铝的复合物中的至少一种，平均粒径D50满足5μm＜D50＜50μm。
  6. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述二乙基次膦酸铝的平均粒径D50满足5μm＜D50＜50μm。
  7. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述含氮化合物无晶型转变特征，包括MPP、MCA、三嗪化合物中的至少一种，平均粒径D50满足5μm＜D50＜50μm。
  8. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述锌盐热稳定化合物无晶型转变特征，包括硼酸锌、氧化锌、锡酸锌中的至少一种，平均粒径D50满足5μm＜D50＜50μm，在所述无卤阻燃剂组合物中的质量百分占比为0～10％。
  9. 根据权利要求1所述的无卤阻燃剂组合物，其特征在于，所述无卤阻燃剂组合物中还包括以下组分(A)-(C)中的至少一种：
    (A)乙基丁基次膦酸盐、丁基丁基次膦酸盐、乙基己基次膦酸盐、丁基己基次膦酸盐、己基己基次膦酸盐中的一种或几种非复合盐；
    (B)烷基亚膦酸盐；
    (C)硫酸盐、氯化物、磷酸盐、亚磷酸盐、次磷酸盐、硝酸盐、乙酸盐、铵盐、含铁化合物、含钙化合物、含镁化合物、含钛化合物、含钠化合物、含钾化合物中的一种或几种。
  10. 根据权利要求1～9任一项所述的无卤阻燃剂组合物在玻纤增强工程塑料阻燃中的应用，其特征在于，所述玻纤增强工程塑料以玻纤增强尼龙、聚酯、POK中的至少一种作为聚合物基体；
    以所述玻纤增强工程塑料的总质量为100％计，所述无卤阻燃剂组合物的添加量为5％～40％，所述玻纤增强工程塑料的阻燃等级达UL94 V-0。
PCT/CN2022/087308 2022-03-10 2022-04-18 无卤阻燃剂组合物及其应用 WO2023168791A1 (zh)

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