A polymer additive, its preparation method and application

Abstract

This invention belongs to the technical field of flame retardants and discloses a polymer additive, its preparation method, and its application. The polymer additive comprises aluminum diethylphosphinate with the structural formula shown in formula (I) and aluminum ethylbutylphosphinate with the structural formula shown in formula (II); the polymer additive satisfies the dual enthalpy ratio ΔH defined by formula (1): 0.92≤ΔH≤1.06; and satisfies 130℃≤T1≤155℃, 165℃≤T2≤185℃; formula (1) ΔH=H2 / H1. The polymer additive has good thermal stability, making it more difficult for the polymer additive to decompose during processing, thus reducing its corrosion of metal processing parts in metal production equipment;

Claims

1. A polymer additive, wherein, The polymer additive comprises aluminum diethylphosphinate with the structural formula shown in formula (I) and aluminum ethylbutylphosphinate with the structural formula shown in formula (II); wherein, by weight percentage, the polymer additive comprises: 97.01% to 98.99% aluminum diethylphosphinate and 1.01% to 2.99% aluminum ethylbutylphosphinate; the polymer additive satisfies the dual enthalpy ratio ΔH defined by formula (1): 0.92 ≤ ΔH ≤ 1.06; and satisfies 130℃ ≤ T1 ≤ 155℃, 165℃ ≤ T2 ≤ 185℃; Formula (1) ΔH = H2 / H1; H1, H2, T1, T2 was obtained using differential scanning calorimetry (DSC). The testing method included the following steps: Under a nitrogen atmosphere, the polymer additive was heated from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min, held at this temperature for 3 minutes, and then cooled to room temperature at a rate of 20°C / min to obtain the cooling curve of the polymer additive; the polymer additive was held at room temperature for 3 minutes and then heated again to a maximum temperature of 300°C at a heating rate of 20°C / min to obtain the second heating curve of the polymer additive; H1 is the peak area formed by the starting and ending temperatures of the exothermic peak on the cooling curve, and T1 is the peak temperature of the exothermic peak on the cooling curve; H2 is the peak area formed by the starting and ending temperatures of the endothermic peak on the second heating curve, and T2 is the peak temperature of the endothermic peak on the second heating curve.

2. The polymer additive according to claim 1, wherein, The polymer additive satisfies the following dual enthalpy ratio ΔH: 0.93≤ΔH≤1.05; the polymer additive satisfies 132℃≤T1≤153℃, 170℃≤T2≤183℃.

3. A method for preparing the polymer additive described in claim 1 or 2, wherein, The preparation method is selected from Method 1, Method 2, or Method 3; wherein Method 1 includes the following steps: a) A water-soluble salt or acid of hypophosphite and an initiator are introduced into a jet circulation reaction system to react with an olefin, adding 2.00 to 2.05 molecules of olefin relative to the P on each water-soluble salt or acid of hypophosphite itself, to obtain an aqueous intermediate containing diethylphosphite; b) The aqueous intermediate reacts with a water-soluble aluminum salt in a metathesis reaction to obtain a polymer additive; wherein, in step b) of Method 1, the mass concentration of diethylphosphite in the aqueous intermediate solution is 20-25%, and the mass concentration of water-soluble aluminum salt in the water-soluble aluminum salt solution is 20-25%; in step b) of Method 1, the pH of the metathesis reaction is 3.0-3.1, and the temperature of the metathesis reaction is 40-45°C; Method 2 includes the following steps: a) Under nitrogen protection, a water-soluble salt or acid of hypophosphite reacts with an olefin in the presence of an initiator at 90–100°C and is kept at this temperature. 2.00 to 2.05 molecules of olefin are added relative to the phosphorus content of each water-soluble salt or acid of hypophosphite, yielding an aqueous intermediate containing diethylphosphite; b) Under stirring, the aqueous intermediate is mixed with a water-soluble aluminum salt at ≤15°C and then heated to 70–95°C and kept at this temperature to obtain a polymer additive; and Method 3 includes the following steps: a) Under nitrogen protection, hypophosphite reacts with an olefin in the presence of an initiator at 90–100°C and is kept at this temperature. 2.00 to 2.05 molecules of olefin are added relative to the phosphorus content of each hypophosphite acid, yielding an aqueous intermediate containing diethylphosphite; b) An aluminum hydroxide gel solution is prepared; c) The aqueous intermediate is added dropwise to the aluminum hydroxide gel solution for reaction, heated to 90–120°C and kept at this temperature for 0.1–5 hours to obtain a polymer additive.

4. The preparation method according to claim 3, wherein, In step a) of Method 1, the pressure of the olefin in the jet circulation reaction system is 0.3 to 3.0 MPa; and / or in step a) of Method 1, the reaction temperature in the jet circulation reaction system is 70 to 150 °C; and / or in step b) of Method 1 or Method 2, or in step c) of Method 3, the molar ratio of diethylphosphonate or diethylphosphonic acid in the intermediate aqueous solution to aluminum ions in the water-soluble aluminum salt is 3:(1 to 1.01).

5. Use of the polymer additive described in claim 1 or 2 in reducing corrosion in metal production equipment.

6. Use of the polymer additive described in claim 1 or 2 as a flame retardant, wherein, The flame retardant is used to impart flame retardancy to at least one of reactive or non-reactive polymers, varnishes, foamed coatings, wood, and other cellulose-containing products, or by impregnation to polyester fabrics and / or pure cellulose fabrics and / or blended cellulose fabrics.

7. Use of the polymer additive of claim 1 or 2 for the preparation of flame-retardant polymer molding materials and / or flame-retardant polymer molded articles.

8. As described in claim 6 or 7, wherein, The polymer additive is used in conjunction with a synergist; the synergist is one or more of the following: melamine phosphate, di(melamine) phosphate, penta(melamine) triphosphate, tri(melamine) diphosphate, tetra(melamine) triphosphate, hexa(melamine) pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, and melamine polyphosphate; or, the synergist is a melamine condensation product; or, the synergist is a low-polyester of tris(hydroxyethyl) isocyanurate / salt and aromatic polycarboxylic acids, benzoguanidine, tris(hydroxyethyl) isocyanurate / salt, allantoin, glycourea, melamine, or cyanuric acid. One or more of melamine, urea cyanurate, dicyandiamide, and guanidine; or, the synergist is a nitrogen-containing phosphate of formula (NH4)yH3-yPO4 or (NH4PO3)z, wherein y is 1 to 3 and z is 1 to 10000; or, the synergist is aluminum phosphite and / or aluminum pyrophosphite; or, the synergist is one or more of zinc borate, zinc carbonate, zinc stannate, zinc basal stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, and magnesium carbonate; or, the synergist is one or more of salts of ethylphosphonic acid, butylphosphonic acid, n-butylphosphonic acid, sec-butylphosphonic acid, and hexylphosphonic acid.

9. The use as described in claim 6 or 7, wherein, Other additives may be used, wherein the other additives are at least one of antioxidants, UV stabilizers, γ-ray stabilizers, hydrolytic stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact modifiers, dyes or pigments.

10. A flame-retardant thermoplastic or thermosetting polymer composite material, wherein, It comprises: 0.5 to 45% by weight of the polymer additive described in claim 1 or 2, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of a synergist and 0 to 55% by weight of a filler or reinforcing material.