CN114539621B - Phosphorus-aluminum salt-containing complex and preparation method and application thereof - Google Patents
Phosphorus-aluminum salt-containing complex and preparation method and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Abstract
The invention discloses a phosphorus-containing aluminum salt complex based on ethyl butyl aluminum phosphinate and a preparation method and application thereof. The aluminum phosphate-containing complex can adjust the crystal transformation of the aluminum diethylphosphinate, change the crystal transformation temperature and the heat absorption/release amount of the aluminum diethylphosphinate, even eliminate the crystal transformation, can be used as a flame retardant and a flame retardant synergist, is applied to the flame retardance of high polymer materials, and reduces the negative effect of the aluminum diethylphosphinate caused by the crystal transformation in some application fields.
Description
Technical Field
The invention relates to the technical field of new materials, and particularly relates to an aluminum phosphate-containing salt complex based on ethyl butyl aluminum phosphinate and capable of adjusting crystal form transformation of aluminum diethylphosphinate, and a preparation method and application thereof. The compound can adjust the crystal form transformation of aluminum diethylphosphinate, change the crystal form transformation temperature and the heat absorption/release amount of the aluminum diethylphosphinate, even eliminate the crystal form transformation, can be used as a flame retardant and a flame retardant synergist, is applied to flame retardance of high polymer materials, and reduces negative effects of the aluminum diethylphosphinate caused by the crystal form transformation in some application fields.
Background
The mesoscopic state of the solid matter includes both crystalline and amorphous aggregate states. In the case of crystalline solid substances, a melting point or a crystal transition temperature generally exists, and is a characteristic temperature of a compound, and is a constant temperature, so that the melting point or the crystal transition temperature of the compound does not generally change even when the compound is mixed with other compounds, and the substance generally undergoes rapid heat change at the melting point or the crystal transition temperature. The melting of the crystal or the transformation process of the crystal form is a physical process, but due to the change of heat, other processes are affected, such as certain reaction processes are affected, and the change of the material dimension is caused. Therefore, the melting point or crystal transition temperature of a crystalline substance is generally an essential property to be paid attention to. The melting point or crystal transition temperature of the crystalline solid can be measured by a Differential Scanning Calorimetry (DSC) method, and further, the DSC can measure the amount of heat absorption/release per unit mass when crystal transition occurs, and the magnitude of the amount of heat absorption/release is also a characteristic parameter of crystal transition.
Diethyl aluminium phosphinate is a widely used halogen-free flame retardant, can be applied to thermoplastic materials such as nylon, polyester, thermoplastic elastomer and the like, and can also be applied to thermosetting materials such as polyurethane, epoxy resin and unsaturated polyester. Aluminum diethylphosphinate is a crystalline compound which has a distinct endothermic peak at about 179 ℃ as found by DSC testing, at which point aluminum diethylphosphinate does not melt, but rather has a crystal transition temperature which is characteristic of aluminum diethylphosphinate. The existence of the crystal transition temperature can affect the applied materials, for example, when the aluminum diethylphosphinate is applied to epoxy resin, the aluminum diethylphosphinate particles are dispersed in the matrix of the epoxy resin, and because the epoxy resin needs to be cured at a certain temperature during molding, and the curing temperature of the epoxy resin is very close to the crystal transition temperature of aluminum diethylphosphinate, the crystal of the aluminum diethylphosphinate is transformed to absorb heat, so that the curing reaction of the resin near the flame retardant particles can be affected, the curing of the epoxy resin is not uniform, and glue particles affecting the appearance and the performance are generated. In some applications with high requirements on dimensional stability, aluminum diethylphosphinate is applied to thermoplastic materials, and in the cooling process of molding, due to volume shrinkage during crystal transformation, large size difference of molded products can be caused, so that the application requirements cannot be met. If the aluminum diethylphosphinate has no crystal transformation, the material has lower molding shrinkage, and the dimensional stability of the molded article can be maintained. Thus, in these applications, it is desirable that the crystal transformation of aluminum diethylphosphinate can be adjusted, the crystal transformation temperature changed, the amount of energy absorbed during the crystal transformation reduced, or no crystal transformation process present, so that adverse effects during the application process can be avoided.
In order to solve the negative influence of the crystal form transformation of the aluminum diethylphosphinate, a method for regulating the crystal form transformation of the aluminum diethylphosphinate needs to be researched, and the crystal form transformation temperature of the aluminum diethylphosphinate is changed and even disappears. Regarding the adjustment of the crystal form transformation, for the small molecule compound, as the crystal form transformation temperature is a characteristic temperature of the compound, no relevant report about changing the crystal form transformation temperature of the small molecule compound is found in the current situation, and particularly no relevant report about the crystal form transformation of aluminum diethylphosphinate is found.
Disclosure of Invention
Aiming at the technical problems, the invention provides an aluminum phosphate-containing complex based on ethyl butyl aluminum phosphinate, which can obviously influence the crystal transformation of aluminum diethyl phosphinate when added into aluminum diethyl phosphinate in a small amount, can reduce the crystal transformation temperature and the heat absorption/release amount under low addition amount, and can disappear when the addition amount is high to a certain degree. Moreover, the addition of the phosphorus-containing aluminum salt complex does not affect the flame retardant property of the diethyl aluminum phosphinate, so that the flame retardant property of the phosphorus-containing aluminum salt complex can meet the requirements of some special fields.
A complex of multiple aluminum phosphorous salts based on ethylbutylphosphinic acid aluminum (hereinafter referred to as "aluminum phosphorous salt complex" or "complex"), comprising:
a phosphorus containing structure of formula (I), and
and one or more phosphorus-containing structures represented by structural formula (II) and/or structural formula (III);
in the formula (II), R 1 、R 2 Each independently selected from H or C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not butyl;
in the formula (III), R 3 Is H or C1-C6 alkyl.
The phosphorus-containing aluminum salt complex is different from a single aluminum salt or a mixture of several aluminum salts, shows different properties, and is a compound with a new structure.
The aluminum phosphate-containing complex can regulate the crystal transformation of aluminum diethylphosphinate, reduce the crystal transformation temperature of the aluminum diethylphosphinate at low dosage, reduce the heat absorption/release amount during the crystal transformation, and make the crystal transformation disappear at higher dosage.
Through research, different proportions of the aluminum ethylbutylphosphinate and the aluminum diethylphosphinate can obtain the aluminum ethylbutylphosphinate-aluminum diethylphosphinate complex according to the preparation process. Further research shows that the ethyl butyl aluminum phosphinate can form a composite aluminum salt with dialkyl aluminum phosphinate, monoalkyl aluminum phosphinate and inorganic aluminum phosphite, and can be compounded with a plurality of different dialkyl aluminum phosphinates, monoalkyl aluminum phosphinates, inorganic aluminum phosphites and the like to obtain a phosphorus-aluminum salt complex, and the components and the proportion of the complex can influence the effect of the complex on regulating and controlling the crystal transformation of the diethyl aluminum phosphinate. However, the aluminum ethylbutylphosphinate cannot be compounded with a compound having a non-phosphorus-containing structure to obtain an aluminum salt complex, and cannot be compounded with other metal cation compounds having a non-aluminum metal cation.
In a preferred embodiment, the complex of aluminum and phosphorous salts has a structure represented by the following formula (IV):
in formula (IV), a, b, c, d, e are molar ratios, a is 0.01-0.99, b, c, d, e are 0-0.99 and are not simultaneously 0, a, b, c, d, e +, d +e =1 1 、R 2 Are each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either one is ethyl, the other is not ethyl or butyl, R 3 Is C1-C6 alkyl.
Formula (IV) shows preferred complexes of ethylbutylphosphinic aluminum with other phosphorus-containing aluminum salts, including aluminum diethylphosphinate, an aluminum dialkylphosphinate other than aluminum ethylbutylphosphinate and aluminum diethylphosphinate, an aluminum monoalkylphosphinate, an inorganic aluminum phosphite, and the like. The aluminum ethylbutylphosphinate may form an aluminum salt complex with one or more phosphorus-containing aluminum salts therein.
In a preferred embodiment, the phosphoaluminate complex has a structure represented by the following formula (V):
in the formula (V), a, b, c and d are molar ratios, a, b, c and d are 0.01-0.97, and a + b + c + d =1 1 、R 2 Are each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When one of them is ethyl, the other is not ethyl or butyl, R 3 Is C1-C6 alkyl.
Formula (V) shows preferred aluminum salt complexes of ethylbutylphosphinic aluminum with other phosphorus-containing aluminum salts, including the phosphorus-containing aluminum salt complexes of the present invention with aluminum diethylphosphinate, an aluminum monoalkylphosphinate, and an inorganic aluminum phosphite.
In a preferred embodiment, the phosphoaluminate complex has a structure represented by the following formula (VI):
in the formula (VI), a, b, c and e are molar ratios, a, b, c and e are 0.01-0.97, and a + b + c + e =1 1 、R 2 Are each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not ethyl and butyl.
Formula (VI) shows preferred aluminum phosphate-containing salt complexes of ethylbutylphosphinic acid with other aluminum phosphate-containing salts, including with aluminum diethylphosphinate, an aluminum dialkylphosphinate other than aluminum ethylbutylphosphinate and aluminum diethylphosphinate, an inorganic aluminum phosphite to form the aluminum phosphate-containing salt complex of the present invention with four aluminum phosphate-containing salts.
In a preferred embodiment, the phosphoaluminate complex has a structure represented by formula (VII):
in the formula (VII), a, c, d and e are molar ratios, a, c, d and e are 0.01-0.97, and a + c + d + e =1 1 、R 2 Are each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When one of them is ethyl, the other is not ethyl or butyl, R 3 Is C1-C6 alkyl.
Formula (VII) shows preferred phosphorous aluminum salt complexes of ethylbutylphosphinic acid aluminum with other phosphorous aluminum salts, including the phosphorous aluminum salt complexes of the present invention with four phosphorous aluminum salts formed with a dialkylphosphinic acid aluminum other than ethylbutylphosphinic acid aluminum and diethylphosphinic acid aluminum, a monoalkylphosphinic acid aluminum, an inorganic phosphorous aluminum salt.
In a preferred embodiment, the complex of aluminum and phosphorous salts has a structure represented by the following formula (VIII):
in formula (VIII), a, b and c are molar ratios, a is 0.01-0.98, b is 0.01-0.98, c is 0.01-0.98, a, b and c += 1 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not ethyl or butyl.
Formula (VIII) shows preferred phosphorus-containing aluminum salt complexes of ethylbutylphosphinic acid with other phosphorus-containing aluminum salts, including the phosphorus-containing aluminum salt complexes of the present invention with aluminum diethylphosphinate, one aluminum dialkylphosphinate other than aluminum ethylbutylphosphinate and aluminum diethylphosphinate, and three phosphorus-containing aluminum salts.
In a preferred embodiment, the aluminophosphate complex has a structure represented by the following formula (IX):
in the formula (IX), a, c and d are molar ratios, a, c and d are 0.01-0.98, and a + c + d =1 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When any one is ethyl, the other is not butyl, R 3 Is H or C1-C6 alkyl.
Formula (IX) shows preferred phosphorus-containing aluminum salt complexes of ethylbutylphosphinic acid aluminum with other phosphorus-containing aluminum salts, including the phosphorus-containing aluminum salt complexes of the present invention with three phosphorus-containing aluminum salts formed with a dialkylphosphinic aluminum salt other than ethylbutylphosphinic aluminum and a monoalkylphosphinic aluminum salt.
In a preferred embodiment, the complex of aluminum and phosphorus salts has a structure represented by the following formula (X):
in the formula (X), a, d and e are molar ratios, a, d and e are 0.01-0.98, and a + d + e =1 3 Is C1-C6 alkyl.
Formula (X) shows preferred phosphorus aluminum salt complexes of ethyl butyl aluminum phosphinate with other phosphorus aluminum salts, including the phosphorus aluminum salt complexes of the present invention with three phosphorus aluminum salts formed with one monoalkylaluminum phosphinate and an inorganic aluminum phosphite.
In a preferred embodiment, the phosphoaluminate complex has a structure represented by the following formula (XI):
in the formula (XI), a and c are molar ratios, a and c are 0.01-0.99, and a + c =1,R 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not butyl.
Formula (XI) shows preferred phosphorous aluminum salt complexes of ethylbutylphosphinic acid aluminum with other phosphorous aluminum salts, including the phosphorous aluminum salt complex of the present invention with two phosphorous aluminum salts formed with one dialkylphosphinic acid aluminum other than ethylbutylphosphinic acid aluminum.
In a preferred embodiment, the phosphoaluminum salt complex has a structure represented by the following formula (XII):
in the formula (XII), a and d are in a molar ratio, a and d are 0.01-0.99, and a + d =1 3 Is H or C1-C6 alkyl.
Formula (XII) shows preferred phosphorus aluminum salt complexes of ethyl butyl aluminum phosphinate with other phosphorus aluminum salts, including phosphorus aluminum salt complexes of the present invention with two phosphorus aluminum salts formed with one monoalkylaluminum phosphinate or inorganic aluminum phosphite.
The invention also provides a preparation method of the phosphorus-containing aluminum salt complex, which comprises the following steps:
(1) Dissolving ethylbutylphosphinic acid and/or soluble ethylbutylphosphinic acid salt containing anionic part of structural formula (I) and other acid and/or soluble salt (phosphorus-containing composite anion donor) which participates in the compounding and contains anionic part of structural formula (II) and/or structural formula (III) in water (a small amount of strong acid can be added or no strong acid can be added in the water), adding aluminium-containing compound (aluminium ion donor), and reacting at 80-90 ℃;
(2) After the reaction is finished, solid-liquid separation is carried out, the solid is taken out, washed and dried, and then the phosphorus-aluminum salt complex is obtained by high-temperature treatment at 180-450 ℃.
The preparation method comprises the following steps:
the soluble salt is usually a sodium 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 that the conductivity of the wash effluent is less than 500. Mu.s/cm.
In the step (1), the phosphorus-containing composite anion donor and the aluminum ion donor can be added according to the molar ratio of complete reaction.
In the step (1), the strong acid comprises concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid and concentrated phosphoric acid, and the addition amount of the strong acid can be 2-5% of the mass of the phosphorus-containing composite anion donor.
When the aluminum-containing compound is insoluble in water, the aluminum-containing compound can be dispersed in water to form a suspension dispersion system, and then the suspension dispersion system reacts with the phosphorus-containing composite anion donor added in an acid form, so that high-concentration strong acid does not need to exist; when the aluminum-containing compound is a water-soluble compound, it is recommended to react in the presence of a strong acid at a high concentration, in which case 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%.
In the step (1), the reaction time may be 1 to 5 hours.
In the step (2):
after the reaction is finished, the pH value of the liquid phase can be controlled to be less than 4 to obtain a solid precipitate; the control of pH can be achieved by adding alkali or metal oxide, etc.;
the drying can adopt various ovens, drying rooms, dryers and the like, and the drying temperature can be 100-130 ℃. The high-temperature treatment is a key step of the preparation process, the treatment process is related to the composition, proportion and treatment amount of the phosphorus-aluminum salt complex, the temperature setting of the high-temperature treatment is a key factor of the high-temperature treatment, and researches show that when the treatment temperature is lower than 180 ℃, the phosphorus-aluminum salt complex cannot be obtained, and the upper limit of the high-temperature treatment temperature is the decomposition temperature of the complex, usually lower than 450 ℃, and the high-temperature treatment process: heating to 180-450 deg.C for 0.5-10 hr for 1-300min.
The high-temperature treatment process of step (2) may be performed under an inert atmosphere (nitrogen atmosphere, rare gas atmosphere, etc.) or under vacuum.
After the step (2), the obtained complex containing phosphorus and aluminum salt may be pulverized to a desired particle size as needed.
It has been found that to obtain the complex containing aluminum phosphate according to the present invention, both steps of the preparation method are indispensable, i.e., the complex containing aluminum phosphate according to the present invention cannot be obtained without high-temperature treatment (including treatment temperature below 180 ℃) or by high-temperature heat treatment after dry-blending of several kinds of aluminum phosphate.
DSC representation is carried out on the phosphorus-containing aluminum salt complex prepared by the invention. Taking an example of a complex of ethylbutylphosphinic acid aluminum (0.7) -diethylphosphinic acid aluminum (0.3) having a molecular structure shown in FIG. 1 (the number indicates the molar ratio of the aluminum complex salt, the same applies hereinafter), the DSC chart is shown in FIG. 2. As can be seen from the DSC chart, the complex of the aluminum ethylbutylphosphinate and the aluminum diethylphosphinate has no crystal form transition peak. Fig. 3 is a DSC diagram of a mixture of aluminum ethylbutylphosphinate and aluminum diethylphosphinate (mixed molar ratio 0.7. From the results, the process according to the present application results in a composite of the new structure shown in fig. 1, unlike the mixture of the two. In the mixture of the two, DSC shows the characteristics of the mixture, the crystal form transition temperature is the crystal form transition temperature of aluminum diethylphosphinate, and the enthalpy value of crystal form transition is reduced due to the reduction of the proportion; in the complex, the characteristic crystal form transformation peak of aluminum diethylphosphinate disappears under the same proportion. Therefore, the composite salt is not a mixture of the two, but a new structure.
Surprisingly, when the small amount of the aluminum phosphate-containing salt complex of the present invention described above is added to aluminum diethylphosphinate, the crystal transformation of aluminum diethylphosphinate can be significantly changed, the crystal transformation temperature can be lowered, the heat absorption/release amount during the crystal transformation can be reduced, and at a certain ratio, the crystal transformation of aluminum diethylphosphinate is found to disappear. FIG. 6 is a DSC of a mixture (8 by weight. As can be seen from the figure, when 8wt% of the complex is added, the crystal form transition temperature of aluminum diethylphosphinate is reduced from 179 ℃ to 171.3 ℃, the crystal form transition of aluminum diethylphosphinate is obviously changed, and the crystal form transition temperature is reduced. Furthermore, it was found that the more the crystal transition temperature decreases with the increase of the addition ratio of the phosphorus-containing aluminum salt complex, the more the crystal transition of aluminum diethylphosphinate disappears when added to 30wt%, i.e., no crystal transition occurs in the temperature range under consideration, and the DSC chart thereof is shown in fig. 7.
Therefore, by using the phosphorus-containing aluminum salt complex, the crystal form transformation of the aluminum diethylphosphinate can be adjusted, the crystal form transformation temperature can be reduced, and even the crystal form transformation of the aluminum diethylphosphinate can not occur. Further research shows that when the aluminum phosphate-containing salt complex is used for adjusting the crystal transformation of aluminum diethylphosphinate, the obtained aluminum phosphate-containing salt complex does not influence the flame retardant property, the mechanical property, the temperature resistance, the migration resistance and other properties of the aluminum diethylphosphinate. Therefore, the phosphorus-aluminum salt-containing complex provided by the invention can realize the adjustment of the crystal transformation of the aluminum diethylphosphinate on the premise of not influencing various performances of the aluminum diethylphosphinate, and achieves the aim of the invention.
The phosphorus-aluminum salt-containing complex is used as an effective component for adjusting diethyl aluminum phosphinate, and the molar content of ethyl butyl aluminum phosphinate (phosphorus-containing structure of structural formula (I)) in the phosphorus-aluminum salt-containing complex is preferably more than 10%, and more preferably not less than 30%. If the crystal transformation of aluminum diethylphosphinate is to be eliminated, it is preferred that the aluminum ethylbutylphosphinate (the phosphorus-containing structure of formula (I)) content of the aluminum phosphorus-containing salt complex is greater than 20 mol%.
The invention also provides application of the phosphorus-containing aluminum salt complex in regulating and controlling the crystal form transformation of aluminum diethylphosphinate.
The invention also provides a method for regulating and controlling the crystal form transformation of aluminum diethylphosphinate, which is characterized in that the aluminum phosphate-containing complex is added into the aluminum diethylphosphinate, so that the crystal form transformation temperature of the aluminum diethylphosphinate is reduced or the crystal form transformation phenomenon of the aluminum diethylphosphinate disappears.
As a general inventive concept, the present invention also provides a compound, which comprises the following components by mass:
0.1 to 50 percent of the phosphorus-containing aluminum salt complex,
50 to 99.9 percent of aluminum diethylphosphinate.
The aluminum phosphate-containing complex is added into aluminum diethylphosphinate to regulate the crystal form conversion, and can be uniformly mixed in a physical dry mixing mode, for example, the crystal form conversion can be completed in a solid mixing machine such as a high-stirring machine, a slow mixing machine, a kneader and the like.
The formulation may further comprise at least one of the following components (a) - (C):
(A) One or more non-composite salts of ethylbutylphosphinate, butylbutylphosphinate, ethylhexylphosphinate, butylhexylphosphinate and hexylhexylphosphinate;
(B) Alkylphosphonous salts;
(C) One or more of sulfate, chloride, phosphate, phosphite, hypophosphite, nitrate, acetate, nitrogen-containing compound, iron-containing compound, calcium-containing compound, magnesium-containing compound, titanium-containing compound, sodium-containing compound and potassium-containing compound.
In the presence of the compounds, the regulation effect of the phosphorus-containing aluminum salt complex on the crystal form transformation of the aluminum diethylphosphinate is not influenced.
The invention also provides the application of the phosphorus-containing aluminum salt complex and the compound. The phosphorus-aluminum salt-containing complex and the compound can be used as a flame retardant or a flame-retardant synergist, and are used for the following steps:
flame retardancy of varnish or foaming paint;
flame retardancy of wood or cellulose-containing products;
preparing the flame-retardant polymer molding material, the flame-retardant polymer film and the flame-retardant polymer fiber.
The flame-retardant polymer molding material, the flame-retardant polymer film and the flame-retardant polymer fiber preferably comprise the following raw materials in percentage by mass of 100 percent:
the flame-retardant system comprises the following components in percentage by mass:
the polymer matrix can be selected from PU (polyurethane), TPE (thermoplastic elastomer), epoxy resin, thermosetting unsaturated polyester, nylon, thermoplastic polyester and POK (polyketone).
In the flame-retardant system, the other flame retardant and flame-retardant synergist can be selected from the following components:
dialkylphosphinic acids and/or salts thereof; condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with polyphosphoric acid or mixtures thereof; a nitrogen-containing phosphate; benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, dicyandiamide and/or guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate and/or zinc stannate; phosphites, hydrogenphosphites or condensates thereof; phosphates and derivatives thereof;
melam, melem, melon, dimelamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate and/or melem polyphosphate and/or mixed poly salts thereof and/or ammonium hydrogen phosphate, ammonium dihydrogen phosphate and/or ammonium polyphosphate;
aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, monophenylphosphinic acid and salts thereof, mixtures of dialkylphosphinic acids and salts thereof with monoalkylphosphinic acids and salts thereof, 2-carboxyethylalkylphosphinic acids and salts thereof, 2-carboxyethylmethylphosphinic acids and salts thereof, 2-carboxyethylarylphosphinic acids and salts thereof, 2-carboxyethylphenylphosphinic acids and salts thereof, DOPO and salts thereof, and adducts on p-benzoquinone.
Compared with the prior art, the invention has the following remarkable technical effects:
the invention provides an aluminum phosphate-containing complex based on ethyl butyl aluminum phosphinate, which can obviously influence the crystal form transformation of aluminum diethylphosphinate when added into the aluminum diethylphosphinate in a small amount, can reduce the crystal form transformation temperature and the heat absorption/release amount under the condition of low addition amount, and can disappear when the addition amount reaches a certain degree. Moreover, the addition of the phosphorus-containing aluminum salt complex does not affect the flame retardant property of the diethyl aluminum phosphinate, so that the flame retardant property of the phosphorus-containing aluminum salt complex can meet the requirements of some special fields.
Drawings
FIG. 1 shows the molecular structure of the complex of ethyl butyl aluminum phosphinate (0.7) -diethyl aluminum phosphinate (0.3);
FIG. 2 is a DSC of the aluminum ethylbutylphosphinate-aluminum diethylphosphinate complex shown in FIG. 1;
FIG. 3 is a DSC of a mixture of aluminum ethylbutylphosphinate and aluminum diethylphosphinate (molar ratio 0.7;
FIG. 4 is a DSC of aluminum ethylbutylphosphinate;
FIG. 5 is a DSC of aluminum diethylphosphinate;
FIG. 6 is a DSC of the mixture formed after addition of the aluminum ethylbutylphosphinate-aluminum diethylphosphinate complex shown in FIG. 1 to aluminum diethylphosphinate in a weight ratio of 8;
FIG. 7 is a DSC of the mixture formed after addition of the aluminum ethylbutylphosphinate-aluminum diethylphosphinate complex shown in FIG. 1 to aluminum diethylphosphinate at a weight ratio of 3.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
DSC test method: a nitrogen atmosphere; temperature rise rate: 10 ℃/min; temperature range: room temperature-300 ℃.
Preparation of complex containing phosphorus-aluminum salt
Example 1 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) Complex as illustrated in FIG. 1
The preparation process comprises the following steps: 120.4g (0.7 mol) of sodium ethylbutylphosphinate and 43.2g (0.3 mol) of sodium diethylphosphinate were dissolved in 381.7g of water in a 2L reactor, and the solutions were thoroughly stirred to obtain a mixed solution of sodium ethylbutylphosphinate and sodium diethylphosphinate. 57g of aluminum sulfate was dissolved in 133g of water in a 500mL beaker, and 4.0g of 98wt% concentrated sulfuric acid was added to the aluminum sulfate solution, followed by stirring and mixing to be uniform, followed by transferring to a dropping funnel. Heating the reaction kettle, raising the temperature to 90 ℃, beginning to dropwise add the aluminum sulfate solution containing the sulfuric acid, finishing dropwise adding within 2 hours, and keeping the temperature to continue the reaction for 1 hour. Filtering while the solution is hot, washing the precipitate for multiple times until the conductivity of the washing effluent is less than 200 mu s/cm, and stopping washing. Transferring the materials to an oven, heating to 120 ℃, drying for 60min, heating the solid to 180 ℃ at the speed of 2 ℃/min, keeping for 60min, heating to 320 ℃ at the speed of 1 ℃/min, keeping for 30min, cooling to normal temperature, discharging to obtain the aluminum ethyl butyl phosphinate (0.7) -aluminum diethyl phosphinate (0.3) complex. The material was pulverized to an average particle size D50 of 42 μm, with a yield of 96.5%. The samples were tested for crystal form transformation by DSC and the results are shown in table 1.
TABLE 1
Example 2 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) Complex
The DSC of the sample was tested as in example 1 except that the high temperature treatment temperature was set at 220 ℃ and the results are shown in Table 1.
EXAMPLE 3 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) Complex
The DSC of the sample was measured as in example 1 except that the high temperature treatment was maintained at the temperature for 60min, and the results are shown in Table 1.
Example 4 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) Complex
The preparation process comprises the following steps: 105g (0.7 mol) of ethylbutylphosphinic acid and 36.6g (0.3 mol) of diethylphosphinic acid were dissolved in 424.8g of water in a 2L reactor, and dissolved by stirring sufficiently to obtain a mixed solution of ethylbutylphosphinic acid and diethylphosphinic acid. 78g of aluminum hydroxide was dispersed in 200g of water in a 500mL beaker and transferred to a dropping funnel. Heating the reaction kettle, raising the temperature to 90 ℃, starting to dropwise add the aluminum hydroxide suspension, completing dropwise addition within 2 hours, adjusting the pH value to 2.6 through aluminum hydroxide solids, and keeping the temperature to continue the reaction for 1 hour. Filtering while the solution is hot, washing the precipitate for multiple times until the conductivity of the washing effluent is less than 200 mu s/cm, and stopping washing. Transferring the materials to an oven, heating to 120 ℃, drying for 60min, heating to 180 ℃ at the speed of 2 ℃/min, keeping for 60min, heating to 320 ℃ at the speed of 1 ℃/min, keeping for 60min, cooling to normal temperature, and discharging to obtain the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) complex. The material was pulverized to have an average particle diameter D50 of 40 μm and a yield of 98.2%, and subjected to DSC test, the results of which are shown in Table 1.
EXAMPLE 5 Synthesis of aluminum ethylbutylphosphinate (0.3) -aluminum diethylphosphinate (0.7) Complex
Same as example 1 except that the ratio of the reaction was adjusted to: the molar ratio of sodium ethylbutylphosphinate to sodium diethylphosphinate was 3. The obtained complex of ethyl butyl aluminum phosphinate (0.3) -diethyl aluminum phosphinate (0.7). DSC was measured, and the results are shown in Table 1.
Example 6 Synthesis of aluminum ethylbutylphosphinate (0.1) -aluminum diethylphosphinate (0.9) Complex
Same as example 1 except that the ratio of the reaction was adjusted to: the molar ratio of sodium ethylbutylphosphinate to sodium diethylphosphinate was 1. The obtained complex of ethyl butyl aluminum phosphinate (0.1) -diethyl aluminum phosphinate (0.9). DSC was measured and the results are shown in Table 1.
Example 7 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum ethylhexylphosphinate (0.1) Complex
Same as example 1 except that sodium ethylhexyl phosphinate was added to the reactants and the ratio of the three reactants was: sodium ethylbutylphosphinate: sodium diethylphosphinate: the molar ratio of sodium ethylhexyl phosphinate is 0.7. The obtained complex of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum ethylhexylphosphinate (0.1). DSC was measured, and the results are shown in Table 1.
Example 8 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.15) -aluminum ethylhexylphosphinate (0.1) -aluminum ethylphosphinite (0.05) Complex
Same as example 7 except that sodium ethyl phosphinate was added to the reactants and the ratios of the four reactants were: sodium ethylbutylphosphinate: sodium diethylphosphinate: sodium ethylhexyl phosphinate: the molar ratio of sodium ethylene phosphinate is 0.7. The obtained complex of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.15) -aluminum ethylhexylphosphinate (0.1) -aluminum ethylphosphinite (0.05). DSC was measured, and the results are shown in Table 1.
Example 9 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.15) -aluminum ethylhexylphosphinate (0.1) -aluminum phosphinate (0.05) Complex
The same as example 7, except that sodium phosphinate was added to the reactants and the ratios of the four reactants were: sodium ethylbutylphosphinate: sodium diethylphosphinate: sodium ethylhexyl phosphinate: the molar ratio of sodium phosphite is 0.7. The obtained complex of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.15) -aluminum ethylhexylphosphinate (0.1) -aluminum phosphinate (0.05). DSC was measured and the results are shown in Table 1.
Example 10 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.1) -aluminum ethylhexylphosphinate (0.1) -aluminum ethylphosphinite (0.05) -aluminum phosphite (0.05) Complex
Same as example 8 except that sodium phosphinate was added to the reactants and the ratio of the five reactants was: sodium ethylbutylphosphinate: sodium diethylphosphinate: sodium ethylhexyl phosphinate: sodium ethylene phosphinate: the molar ratio of sodium phosphite is 0.7. The obtained complex of ethyl butyl aluminum phosphinate (0.7) -diethyl aluminum phosphinate (0.1) -ethyl hexyl aluminum phosphinate (0.1) -ethyl aluminum phosphinate (0.05) -aluminum phosphite (0.05). DSC was measured and the results are shown in Table 1.
EXAMPLE 11 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum ethylhexylphosphinate (0.3) Complex
Same as example 1 except that sodium diethylphosphinate was replaced by sodium ethylhexyl phosphinate in the reactants and the ratio of the two reactants was: sodium ethylbutylphosphinate: the molar ratio of sodium ethylhexyl phosphinate was 0.7. The obtained complex of ethyl butyl aluminum phosphinate (0.7) -ethyl hexyl aluminum phosphinate (0.3). DSC was measured and the results are shown in Table 1.
EXAMPLE 12 Synthesis of aluminum ethylbutylphosphinate (0.7) -Alethylphosphinite (0.3) Complex
Same as example 1 except that sodium diethylphosphinate was replaced by sodium ethylphosphinate in the reactants and the ratio of the two reactants was: sodium ethylbutylphosphinate: the molar ratio of sodium ethyl phosphinate is 0.7. The resulting aluminum ethylbutylphosphinate (0.7) -aluminum ethylphosphinite (0.3) complex. DSC was measured and the results are shown in Table 1.
Example 13 Synthesis of aluminum (0.7) -Alfosinate (0.3) ethylbutylphosphinate Complex
Same as example 1 except that sodium diethylphosphinate was replaced by sodium phosphite in the reactants and the ratio of the two reactants was: sodium ethylbutylphosphinate: mole 0.7 of sodium phosphinate. The obtained aluminum (0.7) -aluminum (0.3) ethylphosphinate complex. DSC was measured and the results are shown in Table 1.
Example 14 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum ethylphosphinite (0.1) Complex
Same as example 7 except that sodium ethylhexyl phosphinate was replaced by sodium ethylphosphinate in the reactants and the ratios of the three reactants were: sodium ethylbutylphosphinate: sodium diethylphosphinate: the molar ratio of sodium ethyl phosphinate is 0.7. The obtained complex of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum ethylphosphinite (0.1). DSC was measured, and the results are shown in Table 1.
Example 15 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum phosphinate (0.1) Complex
Same as example 7 except that sodium ethylhexyl phosphinate was replaced by sodium phosphite in the reactants and the proportions of the three reactants were: sodium ethylbutylphosphinate: sodium diethylphosphinate: the molar ratio of sodium phosphinate is 0.7. The obtained complex of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum phosphinate (0.1). DSC was measured and the results are shown in Table 1.
Example 16 Synthesis of aluminum ethylbutylphosphinate (0.7) -aluminum ethylphosphinate (0.2) -aluminum phosphite (0.1) Complex
The same as example 7 except that sodium diethylphosphinate and sodium ethylhexylphosphinate were not used in the reactants, sodium ethylphosphinate and sodium phosphite were substituted, and the ratio of the three reactants was: sodium ethylbutylphosphinate: sodium ethylene phosphinate: the molar ratio of sodium phosphinate is 0.7. The obtained complex of aluminum (0.7) -ethyl-aluminum (0.2) -aluminum (0.1) -phosphinate was obtained. DSC was measured and the results are shown in Table 1.
Comparative example 1
The DSC of the aluminum ethylbutylphosphinate sample was tested and the results are shown in table 1.
Comparative example 2
The DSC of the aluminum diethylphosphinate samples was tested and the results are shown in table 1.
Comparative example 3
The DSC of the aluminum ethylhexylphosphinate samples was tested and the results are shown in table 1.
Comparative example 4
Samples of aluminum ethylphosphonite were tested for DSC and the results are shown in Table 1.
Comparative example 5
The aluminum phosphite samples were tested for DSC and the results are shown in table 1.
Comparative example 6
Aluminum ethylbutylphosphinate and aluminum diethylphosphinate were mixed uniformly in the phosphorus-containing anion ratio of example 1, and the DSC of the sample was obtained, and the results are shown in Table 1.
Comparative example 7
The prepared sample was tested for DSC as in example 1 except that high temperature heat treatment was not performed, and the results are shown in Table 1.
Comparative example 8
Ethyl butyl aluminum phosphinate and diethyl aluminum phosphinate were uniformly mixed in the proportion of the composite aluminum salt in example 1, and the mixture was subjected to the same high-temperature heat treatment as in example 1, and the obtained sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 9
The prepared sample was subjected to DSC, as in example 7, except that the high temperature heat treatment was not conducted, and the results are shown in Table 1.
Comparative example 10
Aluminum ethylbutylphosphinate, aluminum diethylphosphinate and aluminum ethylhexylphosphinate were uniformly mixed in the proportion of the composite aluminum salt of example 7, and the mixture was subjected to the same high-temperature heat treatment as in example 1, and the obtained sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 11
Ethylbutylphosphinic acid aluminum, diethylphosphinic acid aluminum, ethylhexylphosphinic acid aluminum and ethylphosphinic acid aluminum were mixed uniformly in the same proportion as in example 8 for the composite aluminum salt, and a sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 12
Aluminum ethylbutylphosphinate, aluminum diethylphosphinate, aluminum ethylhexylphosphinate, and aluminum phosphite were mixed uniformly in the same proportion as the composite aluminum salt in example 9, and a sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 13
Aluminum ethylbutylphosphinate, aluminum diethylphosphinate, aluminum ethylhexylphosphinate, aluminum ethylphosphinate, and aluminum phosphite were uniformly mixed in the same proportion as in example 10, and the results of DSC measurement were obtained for samples as shown in Table 1.
Comparative example 14
Aluminum ethylbutylphosphinate and aluminum ethylhexylphosphinate were mixed uniformly in the same proportion as the composite aluminum salt in example 11, and a sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 15
Aluminum ethylbutylphosphinate and aluminum ethylphosphinate were uniformly mixed in the same proportion as the complex aluminum salt in example 12, and a sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 16
Ethyl butyl aluminum phosphinate and aluminum phosphinate were mixed uniformly in the same proportion as the complex aluminum salt in example 13, and the results of DSC measurement were shown in Table 1.
Comparative example 17
Ethylbutylphosphinic acid aluminum, diethylphosphinic acid aluminum and ethylphosphinic acid aluminum were mixed uniformly in the same proportion as the complex aluminum salt of example 14, and a sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 18
Ethyl butyl aluminum phosphinate, diethyl aluminum phosphinate and aluminum phosphinate were mixed uniformly in the same proportion as the complex aluminum salt in example 15, and the results of DSC measurement were obtained for samples as shown in Table 1.
Comparative example 19
Ethylbutylphosphinic acid aluminum, ethylphosphinic acid aluminum and phosphorous aluminum were mixed uniformly in the same proportion as the composite aluminum salt in example 16, and a sample was subjected to DSC measurement, and the results are shown in Table 1.
Comparative example 20
DSC was measured on the prepared sample in the same manner as in example 1 except that aluminum sulfate was changed to zinc sulfate, and the results are shown in Table 1. (Note: melting point temperature of zinc diethylphosphinate was 215 ℃ C.)
Regulation of crystal form of aluminum diethylphosphinate by phosphorus-containing composite aluminum salt
Example 17
To aluminum diethylphosphinate was added 3% (based on 100% by mass of the total mass after mixing, the same applies hereinafter) of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) complex obtained in example 1, followed by mixing, sampling, and DSC measurement, and the results are shown in table 2.
TABLE 2
Example 18
To aluminum diethylphosphinate was added 8% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) complex prepared in example 1, mixed by mixing, and subjected to sampling and DSC measurement, the results of which are shown in Table 2.
Example 19
To diethyl aluminum phosphinate was added 12% of the aluminum ethylbutylphosphinate (0.7) -diethyl aluminum phosphinate (0.3) complex prepared in example 1, mixed, sampled, and DSC-tested, and the results are shown in table 2.
Example 20
To diethyl aluminum phosphinate was added 20% of the aluminum ethylbutylphosphinate (0.7) -diethyl aluminum phosphinate (0.3) complex prepared in example 1, mixed, sampled, and subjected to DSC measurement, and the results are shown in Table 2.
Example 21
To aluminum diethylphosphinate was added 30% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) complex prepared in example 1, mixed by mixing, and subjected to sampling and DSC measurement, and the results are shown in Table 2.
Example 22
To aluminum diethylphosphinate was added 70% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.3) complex prepared in example 1, mixed by mixing, and subjected to sampling and DSC measurement, the results of which are shown in Table 2.
Example 23
To aluminum diethylphosphinate was added 8% of the aluminum ethylbutylphosphinate (0.3) -aluminum diethylphosphinate (0.7) complex prepared in example 5, mixed by mixing, and subjected to sampling by DSC, the results of which are shown in Table 2.
Example 24
To diethyl aluminum phosphinate was added 8% of the aluminum ethylbutylphosphinate (0.1) -diethyl aluminum phosphinate (0.9) complex prepared in example 6, mixed, sampled, and subjected to DSC measurement, and the results are shown in Table 2.
Example 25
To aluminum diethylphosphinate was added 8% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum ethylhexylphosphinate (0.1) complex prepared in example 7, mixed by stirring, and subjected to DSC measurement by sampling, the results of which are shown in Table 2.
Example 26
To aluminum diethylphosphinate was added 8% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.15) -aluminum ethylhexylphosphinate (0.1) -aluminum ethylphosphinite (0.05) complex prepared in example 8, mixed well, and sampled for DSC test, the results of which are shown in Table 2.
Example 27
To diethyl aluminum phosphinate was added 8% of the complex of ethyl butyl aluminum phosphinate (0.7) -diethyl aluminum phosphinate (0.15) -ethylhexyl aluminum phosphinate (0.1) -aluminum phosphite (0.05), and the mixture was mixed, and subjected to sampling and DSC testing, and the results are shown in Table 2.
Example 28
To aluminum diethylphosphinate was added 8% of the complex of aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.1) -aluminum ethylhexylphosphinate (0.1) -aluminum ethylphosphinate (0.05) -aluminum phosphite (0.05), and the mixture was mixed, and subjected to sampling and DSC measurement, and the results are shown in Table 2.
Example 29
To diethyl aluminum phosphinate was added 8% of the complex of ethyl butyl aluminum phosphinate (0.7) -ethyl hexyl aluminum phosphinate (0.3) prepared in example 11, the mixture was mixed, and a sample was taken to measure DSC, and the results are shown in Table 2.
Example 30
To diethyl aluminum phosphinate was added 8% of the aluminum ethylbutylphosphinate (0.7) -aluminum ethylphosphinate (0.3) complex prepared in example 12, followed by mixing, sampling, and DSC measurement, and the results are shown in Table 2.
Example 31
To diethyl aluminum phosphinate was added 8% of the aluminum ethyl butyl phosphinate (0.7) -aluminum phosphinate (0.3) complex prepared in example 13, the mixture was mixed, and sampling was performed to measure DSC, and the results are shown in Table 2.
Example 32
To aluminum diethylphosphinate was added 8% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum ethylphosphinite (0.1) complex prepared in example 14, mixed well, and subjected to sampling test by DSC, the results of which are shown in Table 2.
Example 33
To aluminum diethylphosphinate was added 8% of the aluminum ethylbutylphosphinate (0.7) -aluminum diethylphosphinate (0.2) -aluminum phosphinate (0.1) complex prepared in example 15, and the mixture was mixed, followed by sampling and DSC measurement, and the results are shown in Table 2.
Example 34
To diethyl aluminum phosphinate was added 8% of the aluminum ethyl butylphosphinate (0.7) -aluminum ethyl phosphinate (0.2) -aluminum phosphinate (0.1) complex prepared in example 16, and the mixture was mixed, sampled and subjected to DSC measurement, and the results are shown in Table 2.
Example 35
To diethyl aluminum phosphinate were added 8% of the complex of ethyl butyl aluminum phosphinate (0.7) -diethyl aluminum phosphinate (0.3) prepared in example 1 and 1% of ethyl aluminum phosphinate, and the mixture was mixed, sampled and tested by DSC, and the results are shown in Table 2.
Example 36
To diethyl aluminum phosphinate, 8% of the aluminum ethylbutylphosphinate (0.7) -diethyl aluminum phosphinate (0.3) complex obtained in example 1 and 0.5% of sodium sulfate were added, mixed, sampled and subjected to DSC measurement, and the results are shown in Table 2.
Example 37
To diethyl aluminum phosphinate were added 8% of the aluminum ethyl butyl phosphinate (0.7) -aluminum diethyl phosphinate (0.3) complex prepared in example 1 and 1% of aluminum phosphite, and the mixture was mixed, followed by sampling and DSC measurement, and the results are shown in Table 2.
Comparative example 21
8% of aluminum ethylbutylphosphinate was added to aluminum diethylphosphinate, mixed, sampled and tested by DSC, and the results are shown in Table 2.
Comparative example 22
8% of the sample of comparative example 3 was added to diethyl aluminum phosphinate, mixed, sampled and tested for DSC, and the results are shown in Table 2.
Comparative example 23
8% of the sample of comparative example 4 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 24
8% of the sample of comparative example 5 was added to diethyl aluminum phosphinate, mixed, sampled and tested for DSC, and the results are shown in Table 2.
Comparative example 25
8% of the sample of comparative example 6 was added to aluminum diethylphosphinate, mixed, sampled to test DSC, and the results are shown in Table 2.
Comparative example 26
8% of the sample of comparative example 7 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 27
8% of the sample of comparative example 8 was added to diethyl aluminum phosphinate, mixed, sampled and tested for DSC, and the results are shown in Table 2.
Comparative example 28
8% of the sample of comparative example 9 was added to diethyl aluminum phosphinate, mixed, sampled and tested for DSC, and the results are shown in Table 2.
Comparative example 29
8% of the sample of comparative example 10 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 30
8% of the sample of comparative example 11 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 31
8% of the sample of comparative example 12 was added to aluminum diethylphosphinate, mixed, sampled to test DSC, and the results are shown in Table 2.
Comparative example 32
8% of the sample of comparative example 13 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 33
8% of the sample of comparative example 14 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 34
8% of the sample of comparative example 15 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 35
8% of the sample of comparative example 16 was added to aluminum diethylphosphinate, mixed, sampled to test DSC, and the results are shown in Table 2.
Comparative example 36
8% of the sample of comparative example 17 was added to aluminum diethylphosphinate, mixed, sampled to test DSC, and the results are shown in Table 2.
Comparative example 37
8% of the sample of comparative example 18 was added to diethyl aluminum phosphinate, mixed, sampled to test DSC, and the results are shown in Table 2.
Comparative example 38
8% of the sample of comparative example 19 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
Comparative example 39
8% of the sample of comparative example 20 was added to diethyl aluminum phosphinate, mixed, sampled for DSC, and the results are shown in Table 2.
As seen from the results in Table 1, the complex containing aluminum phosphate produced by the process of the present invention is different from the single phosphorus-containing compound and the mixture thereof involved in the complex. As can be seen from the results in Table 2, the aluminum phosphate-containing complex obtained by the present invention can regulate the crystal transformation of aluminum diethylphosphinate, lower the crystal transformation temperature of aluminum diethylphosphinate, and make the crystal transformation temperature of aluminum diethylphosphinate disappear under certain conditions.
Use of phosphorus-containing aluminum salt complexes
Example 38
Using 50% by weight of high temperature nylon PPA,30% by weight of glass fiber, 20% by weight of the inventive aluminophosphate composite according to example 1, flame retardant glass fiber reinforced PPA was prepared according to the general protocol, and the flame retardancy was tested as a sample, the material flame retardancy reached UL 94V 0 (0.8 mm), and the shrinkage was 0.25%.
Example 39
Using 50% by weight of high temperature nylon PPA,30% by weight of glass fiber, 20% by weight of the mixture of aluminum diethylphosphinate and the aluminum phosphorous salt complex according to example 17, flame retardant glass fiber reinforced PPA was prepared according to the general protocol and tested for flame retardant properties by making samples, the material flame retardant reached UL 94V 0 (0.8 mm) with a shrinkage of 0.30%.
Comparative example 40
Using 50% by weight of high temperature nylon PPA,30% by weight of glass fiber, 20% by weight of the mixture of aluminum diethylphosphinate and aluminum ethylbutylphosphinate of comparative example 21, flame retardant glass fiber reinforced PPA was prepared according to the general protocol, and the flame retardancy was tested by sample preparation to achieve UL 94V 0 (0.8 mm) and 0.6% shrinkage.
Comparative example 41
The flame retardant glass fiber reinforced PPA was prepared according to the general protocol using 50% by weight of high temperature nylon PPA,30% by weight of glass fiber, 20% by weight of aluminum diethylphosphinate, and the flame retardant performance was tested as a sample, with the material flame retardant reaching UL 94V 0 (0.8 mm) and the shrinkage being 0.6%.
From the application results, it can be seen that the phosphorus-containing aluminum salt composite and the mixture of the aluminum salt composite and aluminum diethylphosphinate have good flame retardance, and the shrinkage rate of the material can be obviously reduced.
Example 40
An epoxy copper clad laminate (FCCL) was prepared and characterized as follows:
1) The halogen-free flame-retardant epoxy resin composition is prepared by blending the following raw materials according to the following formula in parts by mass:
butanone solvent is used for adjusting the solid content of the glue solution to 40 percent, and the halogen-free flame retardant epoxy resin composition is prepared by mixing.
2) Coating the halogen-free flame-retardant epoxy resin composition prepared in the step 1) on a polyimide insulating film with the thickness of 12.5 micrometers by a glue coating machine, coating the glue with the thickness of 13 micrometers, heating the glue in a drying oven at 180 ℃ for 3 minutes to form a partially cured composition layer on the polyimide thin insulating film, then coating the partially cured composition layer on release paper, and rolling to obtain the high-flexibility halogen-free flame-retardant covering film.
And (3) performance test results: the flame retardant performance passes the UL94 V0 test; the appearance of the adhesive film has no adhesive particles.
Example 41
The procedure was followed as in example 40 except that the formulation was changed to a mixture of aluminum diethylphosphinate and the aluminum phosphorous salt complex of example 17 for the flame retardant component of example 1. And (3) performance test results: the flame retardant performance passes the UL94 V0 test; the appearance of the adhesive film has no adhesive particles.
Comparative example 42
The procedure was carried out as in example 40, except that the phosphorus-containing aluminum salt complex of example 1 was replaced in the formulation system with the mixture of aluminum diethylphosphinate and aluminum ethylbutylphosphinate of comparative example 21. And (3) performance test results: the flame retardant performance passes the UL94 V0 test; the appearance of the adhesive film has adhesive particles.
Comparative example 43
The procedure was as in example 40, except that the aluminum phosphate-containing salt complex of example 1 was replaced with aluminum diethylphosphinate in the formulation. And (3) performance test results: the flame retardant performance passes the UL94 V0 test; the appearance of the adhesive film has adhesive particles.
As can be seen from the application results, the phosphorus-containing aluminum salt complex and the mixture of the aluminum salt complex and aluminum diethylphosphinate of the present invention have good flame retardancy, and at the same time, the colloidal particle condition can be significantly improved.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (21)
1. A plurality of aluminum phosphate-containing complexes based on aluminum ethylbutylphosphinate, the complexes comprising:
a phosphorus-containing structure of formula (I), and
one or more phosphorus-containing structures represented by structural formula (II) and/or structural formula (III);
in the formula (II), R 1 、R 2 Each independently selected from H or C1-C6 alkyl, and when R 1 、R 2 When either is ethyl, the other is not butyl;
in the formula (III), R 3 Is H or C1-C6 alkyl.
2. The composite of claim 1, wherein the composite has a structure according to formula (IV) below:
in formula (IV), a, b, c, d, e are molar ratios, a is 0.01-0.99, b, c, d, e are 0-0.99 and are not simultaneously 0, a, b, c, d, e +, d +e =1 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When one of them is ethyl, the other is not ethyl or butyl, R 3 Is C1-C6 alkyl.
3. The composite of claim 2, wherein the composite has a structure represented by formula (V) below:
in the formula (V), a, b, c and d are molar ratios, a, b, c and d are 0.01-0.97, and a + b + c + d =1 1 、R 2 Are each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When one of them is ethyl, the other is not ethyl or butyl, R 3 Is C1-C6 alkyl.
4. The composite of claim 2, wherein the composite has a structure according to formula (VI):
in the formula (VI), a, b, c and e are molar ratios, a, b, c and e are 0.01-0.97, and a + b + c + e =1 1 、R 2 Are each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not ethyl and butyl.
5. The composite of claim 2, wherein the composite has a structure according to formula (VII):
in the formula (VII), a, c, d and e are molar ratios, a, c, d and e are 0.01-0.97, and a + c + d + e =1 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either one is ethyl, the other is not ethyl or butyl, R 3 Is C1-C6 alkyl.
6. The composite of claim 2, wherein the composite has a structure according to formula (VIII) below:
in formula (VIII), a, b and c are molar ratios, a is 0.01-0.98, b is 0.01-0.98, c is 0.01-0.98, a, b and c += 1 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not ethyl or butyl.
7. The complex of claim 1, wherein the complex has a structure represented by formula (IX):
in the formula (IX), a, c and d are molar ratios, a, c and d are 0.01-0.98, and a + c + d =1 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not butyl, R 3 Is H or C1-C6 alkyl.
8. The composite of claim 2, wherein the composite has a structure represented by formula (X):
in the formula (X), a, d and e are molar ratios, a, d and e are 0.01-0.98, and a + d + e =1 3 Is C1-C6 alkyl.
9. The composite of claim 1, wherein the composite has a structure according to formula (XI):
in the formula (XI), a and c are molar ratios, a and c are 0.01-0.99, and a + c =1,R 1 、R 2 Each independently selected from C1-C6 alkyl, and when R is 1 、R 2 When either is ethyl, the other is not butyl.
10. The composite of claim 1, wherein the composite has the structure shown in formula (XII) below:
in the formula (XII), a and d are in a molar ratio, a and d are 0.01-0.99, and a + d =1 3 Is H or C1-C6 alkyl.
11. A method of preparing the composite body according to claim 1, comprising the steps of:
(1) Dissolving ethylbutylphosphinic acid and/or soluble ethylbutylphosphinic acid salt containing anion part of structural formula (I) and other acid and/or soluble salt participating in compounding and containing anion part of structural formula (II) and/or structural formula (III) in water, adding aluminum-containing compound, and reacting at 80-90 ℃;
(2) After the reaction is finished, solid-liquid separation is carried out, the solid is taken out, washed and dried, and then the complex is obtained by high-temperature treatment at 180-450 ℃.
12. Use of a complex according to any one of claims 1-10 to modulate the crystal form transition of aluminum diethylphosphinate.
13. A method for regulating crystal form transition of aluminum diethylphosphinate, characterized in that the complex according to any one of claims 1 to 10 is added to aluminum diethylphosphinate, so that the crystal form transition temperature of aluminum diethylphosphinate is lowered or the crystal form transition phenomenon of aluminum diethylphosphinate is eliminated.
14. A compound is characterized by comprising the following components in percentage by mass:
0.1% to 50% of the composite of any one of claims 1 to 10,
50 to 99.9 percent of aluminum diethylphosphinate.
15. The formulation according to claim 14, further comprising at least one of the following components (a) - (C):
(A) One or more non-composite salts of ethylbutylphosphinate, butylbutylphosphinate, ethylhexylphosphinate, butylhexylphosphinate and hexylhexylphosphinate;
(B) Alkylphosphonous salts;
(C) One or more of sulfate, chloride, phosphate, phosphite, hypophosphite, nitrate, acetate, nitrogen-containing compound, iron-containing compound, calcium-containing compound, magnesium-containing compound, titanium-containing compound, sodium-containing compound and potassium-containing compound.
16. Use of a composite according to any of claims 1 to 10 as a flame retardant or flame retardant synergist for a composition comprising:
flame retardancy of varnish or foamed coating;
flame retardancy of wood or cellulose-containing products;
preparing the flame-retardant polymer molding material, the flame-retardant polymer film and the flame-retardant polymer fiber.
17. The use according to claim 16, wherein the flame retardant polymer molding material, the flame retardant polymer film and the flame retardant polymer fiber comprise, based on 100% by mass of the total composition, the raw materials:
the flame retardant system comprises the following components in percentage by mass:
1 to 100 percent of the complex body,
0-99% of other flame-retardant synergist.
18. Use according to claim 17, wherein said polymeric matrix is selected from the group consisting of polyurethane, thermoplastic elastomer, epoxy resin, thermosetting unsaturated polyester, nylon, thermoplastic polyester, POK.
19. Use of a formulation according to claim 14 as flame retardant or flame retardant synergist for comprising:
flame retardancy of varnish or foamed coating;
flame retardancy of wood or cellulose-containing products;
preparing the flame-retardant polymer molding material, the flame-retardant polymer film and the flame-retardant polymer fiber.
20. The use according to claim 19, wherein the flame retardant polymer molding material, the flame retardant polymer film and the flame retardant polymer fiber comprise, based on 100% by mass of the total composition, the raw materials:
the flame-retardant system comprises the following components in percentage by mass:
1 to 100 percent of the compound,
0-99% of other flame-retardant synergist.
21. Use according to claim 20, wherein said polymeric matrix is selected from the group consisting of polyurethane, thermoplastic elastomer, epoxy resin, thermosetting unsaturated polyester, nylon, thermoplastic polyester, POK.
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| CN202210231009.8A CN114539621B (en) | 2022-03-10 | 2022-03-10 | Phosphorus-aluminum salt-containing complex and preparation method and application thereof |
| PCT/CN2022/087340 WO2023168792A1 (en) | 2022-03-10 | 2022-04-18 | Phosphorus-containing aluminum salt complex and preparation method therefor and application thereof |
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| CN202210231009.8A CN114539621B (en) | 2022-03-10 | 2022-03-10 | Phosphorus-aluminum salt-containing complex and preparation method and application thereof |
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| CN114478625B (en) * | 2022-03-10 | 2022-11-25 | 江苏利思德新材料股份有限公司 | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application thereof |
| CN115819844A (en) * | 2022-12-05 | 2023-03-21 | 金发科技股份有限公司 | Alkyl phosphonous acid composite salt and preparation method and application thereof |
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| CN109851852A (en) * | 2018-12-28 | 2019-06-07 | 江苏利思德新材料有限公司 | A kind of dialkylphosphinic salts composition of low-corrosiveness and its application |
| CN112876736A (en) * | 2020-09-01 | 2021-06-01 | 黎杰 | Dialkyl phosphinic acid-aluminum phosphite composite salt, preparation method and application thereof |
| CN113460984A (en) * | 2020-10-22 | 2021-10-01 | 江苏利思德新材料有限公司 | Crystalline aluminum phosphite and preparation method and application thereof |
| WO2021254907A1 (en) * | 2020-06-15 | 2021-12-23 | Clariant International Ltd | Flame retardant-stabilizer combination for thermoplastic polymers |
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| JP4581642B2 (en) * | 2004-11-18 | 2010-11-17 | 日立化成工業株式会社 | Metal-clad laminate and printed wiring board |
| DE102016213281A1 (en) * | 2016-07-20 | 2018-01-25 | Clariant Plastics & Coatings Ltd | Flame retardant mixtures, their preparation and their use |
| CN111662323A (en) * | 2019-03-07 | 2020-09-15 | 黎杰 | Dialkyl phosphinic acid-alkyl phosphorous acid metal composite salt, preparation method and application thereof |
| CN111825883A (en) * | 2019-04-15 | 2020-10-27 | 黎杰 | Metal complex salts of polydialkylphosphinic acids and/or mixtures thereof, and use thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109851852A (en) * | 2018-12-28 | 2019-06-07 | 江苏利思德新材料有限公司 | A kind of dialkylphosphinic salts composition of low-corrosiveness and its application |
| WO2021254907A1 (en) * | 2020-06-15 | 2021-12-23 | Clariant International Ltd | Flame retardant-stabilizer combination for thermoplastic polymers |
| CN112876736A (en) * | 2020-09-01 | 2021-06-01 | 黎杰 | Dialkyl phosphinic acid-aluminum phosphite composite salt, preparation method and application thereof |
| CN113460984A (en) * | 2020-10-22 | 2021-10-01 | 江苏利思德新材料有限公司 | Crystalline aluminum phosphite and preparation method and application thereof |
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