Flame-retardant low-smoke masterbatch and its preparation method and application

Abstract

The present invention belongs to the technical field of flame retardant modification of plastics, and relates to a flame retardant low-smoke masterbatch and its preparation method and application. The present invention reacts a polyethylene diamine triazine ring derivative and sodium hypophosphite under the catalysis of an acid to generate a salt, and the obtained salt is compounded with polyphosphoamine to obtain a phosphorus-nitrogen compound flame retardant; a thermoplastic plastic and a plasticizer are mixed to obtain a plastic mixture; a stabilizer and a plasticizer are mixed to obtain a slurry; the plastic mixture, slurry, active magnesium hydroxide, wollastonite, a phosphorus-nitrogen compound flame retardant and a dispersant are mixed to obtain a primary mixture; the obtained primary mixture is extruded and granulated to obtain a flame retardant low-smoke masterbatch. The phosphorus-nitrogen compound flame retardant in the present invention works synergistically with magnesium hydroxide and wollastonite with excellent smoke suppression properties to achieve flame retardancy and smoke suppression. The masterbatch made of this material can be used to prepare various plastic products, and the plastic products can meet V0 grade requirements and have low smoke emission.

Description

Technical Field

[0001] The present invention relates to the technical field of flame retardant modification of plastics, in particular to a flame retardant low-smoke masterbatch and a preparation method and application thereof. Background Art

[0002] With the large-scale application of plastic products, the potential fire hazard has greatly increased due to their poor heat resistance and flame retardancy, especially for materials in closed systems. Once a fire occurs, the smoke cannot be effectively diffused, which can easily cause suffocation and death. Therefore, the development of flame-retardant and low-smoke materials is urgent. Summary of the Invention

[0003] The purpose of the present invention is to provide a flame retardant low smoke masterbatch and a preparation method and application thereof, so as to make up for the deficiencies of the prior art.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a flame-retardant low-smoke masterbatch, comprising the following steps:

[0006] Polyethylenediamine triazine ring derivative and sodium hypophosphite are reacted under acid catalysis to form phosphazenium salt;

[0007] mixing a thermoplastic and a plasticizer to obtain a plastic mixture;

[0008] Mixing a stabilizer and a plasticizer to obtain a slurry, or mixing a stabilizer, a plasticizer and a colorant to obtain a slurry;

[0009] The plastic mixture, slurry, active magnesium hydroxide, wollastonite, phosphorus nitrogen flame retardant and dispersant are mixed to obtain a primary mixture; the phosphorus nitrogen flame retardant is a phosphorus nitrogen salt or a mixture of a phosphorus nitrogen salt and polyphosphate amine.

[0010] The obtained primary mixture is extruded and granulated to obtain flame retardant low smoke masterbatch.

[0011] Preferably, the polyethylenediamine triazine ring derivative comprises one or more of a polyethylenediamine triazine ring, a phenoxy polyethylenediamine triazine ring, a hydroxy polyethylenediamine triazine ring, an ester polyethylenediamine triazine ring and a silicone polyethylenediamine triazine ring;

[0012] The molar ratio of the polyethylenediamine triazine ring derivative, acid and sodium hypophosphite is 1:(0.8-1.2):(0.8-1.2);

[0013] The acid comprises hydrochloric acid or sulfuric acid with a concentration of 1 to 100 mol / L;

[0014] The reaction temperature is 20-60°C and the reaction time is 1-24h;

[0015] The mass ratio of the phosphorus nitrogen salt to the polyphosphoric acid amine is 1:2-4.

[0016] Preferably, the thermoplastic plastic comprises one or more of polyethylene, polypropylene, polymethyl methacrylate, ethylene-vinyl acetate copolymer, polyacrylonitrile, and polystyrene;

[0017] The plasticizer is a main plasticizer, or a mixture of a main plasticizer and an auxiliary plasticizer;

[0018] The main plasticizer includes one or two of a phthalate plasticizer and a phosphate plasticizer, the phthalate plasticizer includes dioctyl phthalate or dibutyl phthalate, and the phosphate plasticizer includes tricresyl phosphate;

[0019] The secondary plasticizer comprises epoxidized soybean oil;

[0020] The mass ratio of the thermoplastic plastic to the plasticizer is 50-60:3-10.

[0021] Preferably, the stabilizer comprises one or more of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;

[0022] The mass ratio of the stabilizer to the plasticizer is (1-3): (1-9).

[0023] Preferably, the mass ratio of the plastic mixture, slurry, magnesium hydroxide, wollastonite, phosphorus-nitrogen compound flame retardant and dispersant is (50-65): (1-5): (20-35): (5-8): (3-7): (1-3), wherein magnesium hydroxide is the raw material for preparing active magnesium hydroxide.

[0024] Preferably, the dispersant comprises an inorganic dispersant or an organic dispersant;

[0025] The inorganic dispersant includes a silicate dispersant and / or an alkali metal phosphate dispersant;

[0026] The organic dispersant includes one or more of triethylhexyl phosphate, cellulose derivatives, sodium lauryl sulfate and fatty acid polyethylene glycol ester.

[0027] Preferably, the extrusion granulation process is divided into three zones, the temperature of zone one is 130-170°C, the temperature of zone two is 160-190°C, and the temperature of zone three is 140-150°C.

[0028] The present invention also provides flame-retardant low-smoke masterbatch obtained by the preparation method.

[0029] The present invention also provides the use of the flame-retardant low-smoke masterbatch in the preparation of flame-retardant low-smoke plastic products or wires and cables.

[0030] Beneficial effects of the present invention:

[0031] The phosphorus-nitrogen composite flame retardant of the present invention cooperates with magnesium hydroxide and wollastonite with excellent smoke suppression to achieve flame retardancy and smoke suppression. The masterbatch made of the material can be used to prepare various plastic products. The plastic products can meet V0 grade requirements and have low smoke emission. DETAILED DESCRIPTION

[0032] The present invention provides a method for preparing a flame-retardant low-smoke masterbatch, comprising the following steps:

[0033] Polyethylenediamine triazine ring derivative and sodium hypophosphite are reacted under acid catalysis to form phosphazenium salt;

[0034] mixing a thermoplastic and a plasticizer to obtain a plastic mixture;

[0035] Mixing a stabilizer and a plasticizer to obtain a slurry, or mixing a stabilizer, a plasticizer and a colorant to obtain a slurry;

[0036] The plastic mixture, slurry, active magnesium hydroxide, wollastonite, phosphorus nitrogen flame retardant and dispersant are mixed to obtain a primary mixture; the phosphorus nitrogen flame retardant is a phosphorus nitrogen salt or a mixture of a phosphorus nitrogen salt and polyphosphate amine.

[0037] The obtained primary mixture is extruded and granulated to obtain flame retardant low smoke masterbatch.

[0038] In the present invention, the polyethylenediamine triazine ring derivative comprises one or more of polyethylenediamine triazine ring, phenoxy polyethylenediamine triazine ring, hydroxy polyethylenediamine triazine ring, ester polyethylenediamine triazine ring and silicone polyethylenediamine triazine ring;

[0039] The molar ratio of the polyethylenediamine triazine ring derivative, acid and sodium hypophosphite is 1:(0.8-1.2):(0.8-1.2), preferably 1:(0.9-1.1):(0.9-1.1), and more preferably 1:1:1;

[0040] The acid comprises hydrochloric acid or sulfuric acid, with a concentration of 1 to 100 mol / L, preferably 1 to 90 mol / L, and more preferably 1 to 50 mol / L;

[0041] The reaction temperature is 20-60°C, preferably 30-50°C, more preferably 40-45°C; the reaction time is 1-24h, preferably 1-5h, more preferably 1h;

[0042] The mass ratio of the phosphorus nitrogen salt to the polyphosphoric acid amine is 1:2-4, preferably 1:3.

[0043] In the present invention, the thermoplastic plastic comprises one or more of polyethylene, polypropylene, polymethyl methacrylate, ethylene-vinyl acetate copolymer, polyacrylonitrile, and polystyrene;

[0044] The plasticizer is a main plasticizer, or a mixture of a main plasticizer and an auxiliary plasticizer;

[0045] The main plasticizer includes one or two of a phthalate plasticizer and a phosphate plasticizer, the phthalate plasticizer includes dioctyl phthalate or dibutyl phthalate, and the phosphate plasticizer includes tricresyl phosphate;

[0046] The secondary plasticizer comprises epoxidized soybean oil;

[0047] The mass ratio of the thermoplastic plastic to the plasticizer is 50-60:3-10, preferably 52-58:4-9, and more preferably 54-56:5-7;

[0048] The mixing machine can be a ribbon mixer, a kneader, or a high-speed mixer.

[0049] In the present invention, the preparation method of the active magnesium hydroxide comprises the following steps:

[0050] Mixing magnesium hydroxide and a coupling agent solution, stirring, drying, and grinding in sequence to obtain active magnesium hydroxide;

[0051] The stirring rate is 300-1000 r / min, preferably 350-500 r / min, more preferably 400-420 r / min; the stirring time is 30-60 min, preferably 35-55 min, more preferably 40-50 min;

[0052] The concentration of the coupling agent solution is 80 to 120 mol / L, preferably 90 to 110 mol / L, and more preferably 100 mol / L; the coupling agent solution comprises an aqueous solution of dodecyl phosphate;

[0053] The drying temperature is 100-105°C, preferably 101-103°C;

[0054] The usage ratio of the magnesium hydroxide and the coupling agent solution is 20 g: 20-40 mL.

[0055] In the present invention, the stabilizer comprises one or more of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;

[0056] The mass ratio of the stabilizer to the plasticizer is (1-3): (1-9), preferably (1-3): (1-6), and more preferably (1-3): (1-3).

[0057] In the present invention, the mass ratio of the plastic mixture, slurry, magnesium hydroxide, wollastonite, phosphorus-nitrogen compound flame retardant and dispersant is (50-65): (1-5): (20-35): (5-8): (3-7): (1-3), wherein magnesium hydroxide is the raw material for preparing active magnesium hydroxide.

[0058] In the present invention, the dispersant comprises an inorganic dispersant or an organic dispersant;

[0059] The inorganic dispersant includes a silicate dispersant and / or an alkali metal phosphate dispersant;

[0060] The organic dispersant includes one or more of triethylhexyl phosphate, cellulose derivatives, sodium lauryl sulfate and fatty acid polyethylene glycol ester.

[0061] In the present invention, the extrusion granulation process is divided into three zones, the temperature of zone one is 130-170°C, preferably 140-160°C, and more preferably 150-155°C; the temperature of zone two is 160-190°C, preferably 170-180°C, and more preferably 175-177°C; the temperature of zone three is 140-150°C, preferably 142-147°C, and more preferably 145°C.

[0062] The present invention also provides flame-retardant low-smoke masterbatch obtained by the preparation method.

[0063] The present invention also provides the use of the flame-retardant low-smoke masterbatch in the preparation of flame-retardant low-smoke plastic products or wires and cables.

[0064] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0065] Example 1

[0066] Polyethylenediamine triazine ring reacts with 1 mol / L dilute hydrochloric acid and sodium hypophosphite in a molar ratio of 1:1:1 at 20°C for 1 hour to produce a phosphorus-nitrogen flame retardant. 59 parts of polypropylene powder are placed in a high-speed mixer and stirred. During the stirring process, 3 parts of dibutyl phthalate are sprayed in. One part of the stabilizer, 2,6-di-tert-butyl-4-methylphenol, is dissolved in one part of dibutyl phthalate to form a slurry, which is added to the polypropylene powder. 25 parts (g) of magnesium hydroxide are then added to 37.5 mL of a 100 mol / L aqueous solution of methyl dodecyl phosphate. The mixture is stirred at 300 rpm for 30 minutes, dried, ground into a fine powder, and added to a blender. Five parts of wollastonite powder, five parts of a phosphorus-nitrogen composite flame retardant, and two parts of a dispersant, triethylhexyl phosphoric acid, are then added to the blender and stirred for 30 minutes to produce a preliminary mixture. The initial mixture was placed into the extruder feed port. The temperatures in zone 1 were set at 140°C, zone 2 at 185°C, and zone 3 at 150°C. The material was plasticized and extruded into pellets to produce a flame-retardant, low-smoke masterbatch. Samples of this masterbatch were then tested for flame retardancy, and the results were confirmed to pass the UL94 V0 rating and a smoke density rating of 35.8.

[0067] Example 2

[0068] Polyethylenediamine triazine ring reacts with 1 mol / L dilute sulfuric acid and sodium hypophosphite in a molar ratio of 1:1:1 at 60°C for 1 hour to produce a phosphorus-nitrogen flame retardant. 51 parts of polyethylene powder are placed in a high-speed mixer and stirred. During stirring, 3 parts of dibutyl phthalate are sprayed in. One part of the stabilizer, 2,6-di-tert-butyl-4-methylphenol, is dissolved in one part of dibutyl phthalate to form a slurry, which is added to the polypropylene powder. 30 parts (g) of magnesium hydroxide are added to 45 mL of a 100 mol / L aqueous solution of methyl dodecyl phosphate and stirred at 500 rpm for 30 minutes. The mixture is dried, ground into a fine powder, and added to a blender. Eight parts of wollastonite powder, five parts of a phosphorus-nitrogen composite flame retardant, and two parts of a dispersant, triethylhexyl phosphoric acid, are then added to the blender and stirred for 30 minutes to produce a preliminary mixture. The initial mixture was placed into the extruder feed port. The temperatures in zone 1 were set at 140°C, zone 2 at 185°C, and zone 3 at 150°C. The material was plasticized and extruded into pellets to produce a flame-retardant, low-smoke masterbatch. Samples of this masterbatch were then tested for flame retardancy, and the results were confirmed to pass the UL94 V0 rating and a smoke density rating of 32.4.

[0069] Example 3

[0070] Phenoxypolyethylenediamine triazine ring reacts with 1 mol / L dilute hydrochloric acid and sodium hypophosphite in a 1:1:1 molar ratio at 45°C for 1 hour to produce a phosphorus-nitrogen flame retardant, which is then combined with ammonium polyphosphate in a 1:3 ratio to form a phosphorus-nitrogen composite flame retardant. 40 parts of polypropylene powder and 11 parts of styrene are placed in a high-speed mixer and stirred. During the stirring process, 3 parts of dibutyl phthalate are sprayed into the mixture. A slurry was prepared by dissolving 1 part of the stabilizer 2,6-di-tert-butyl-4-methylphenol in 1 part of dibutyl phthalate. This slurry was then added to polypropylene powder. 30 parts (g) of magnesium hydroxide was then added to 45 mL of a 100 mol / L aqueous solution of methyl dodecyl phosphate. The mixture was stirred at 350 rpm for 40 minutes, dried, ground into a fine powder, and added to a blender. Eight parts of wollastonite powder, five parts of a phosphorus-nitrogen composite flame retardant, and two parts of a dispersant, sodium lauryl sulfate, were then added to the blender and stirred for 30 minutes to obtain a preliminary mixture. This preliminary mixture was placed into the feed port of an extruder, with the temperatures set at 145°C in zone one, 185°C in zone two, and 150°C in zone three. The material was plasticized and extruded into pellets to produce a flame-retardant, low-smoke masterbatch. Samples of this masterbatch were flame-retardant tested and passed the UL94 V0 rating with a smoke density of 33.2.

[0071] Example 4

[0072] Phenoxypolyethylenediamine triazine ring reacts with 1 mol / L dilute sulfuric acid and sodium hypophosphite in a 1:1:1 molar ratio at 30°C for 1 hour to produce a phosphorus-nitrogen flame retardant, which is then combined with ammonium polyphosphate in a 1:3 ratio to form a composite flame retardant. 40 parts of polypropylene powder and 11 parts of ethylene-vinyl acetate copolymer are placed in a high-speed mixer and stirred. During the stirring process, 3 parts of dibutyl phthalate are sprayed in. A slurry was prepared by dissolving 1 part of the stabilizer 2,6-di-tert-butyl-4-methylphenol in 1 part of dibutyl phthalate. This slurry was then added to polypropylene powder. 30 parts (g) of magnesium hydroxide were then added to 45 mL of a 100 mol / L aqueous solution of methyl dodecyl phosphate. The mixture was stirred at 500 rpm for 30 minutes, dried, ground into a fine powder, and added to a blender. Eight parts of wollastonite powder, five parts of a phosphorus-nitrogen composite flame retardant, and two parts of a dispersant, triethylhexyl phosphate, were then added to the blender and stirred for 30 minutes to obtain a preliminary mixture. This preliminary mixture was placed into the feed port of an extruder, with the temperatures set at 145°C in zone one, 185°C in zone two, and 150°C in zone three. The material was plasticized and extruded into pellets to produce a flame-retardant, low-smoke masterbatch. Samples of this masterbatch were flame-retardant tested and passed the UL94 V0 rating with a smoke density of 31.8.

[0073] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a flame retardant low smoke masterbatch, characterized in that: The following steps are included: A polyethylene diamine triazine ring derivative and sodium hypophosphite are reacted under the catalysis of an acid to generate a phosphonitrogen salt; the polyethylene diamine triazine ring derivative comprises one or more of a polyethylene diamine triazine ring, a phenoxy polyethylene diamine triazine ring, a hydroxy polyethylene diamine triazine ring, an ester polyethylene diamine triazine ring, and a siloxane polyethylene diamine triazine ring; the molar ratio of the polyethylene diamine triazine ring derivative, the acid, and the sodium hypophosphite is 1:(0.8-1.2):(0.8-1.2); the acid comprises hydrochloric acid or sulfuric acid at a concentration of 1-100 mol / L; the reaction temperature is 20-60° C., and the reaction time is 1-24 hours; mixing a thermoplastic and a plasticizer to obtain a plastic mixture; Mixing a stabilizer and a plasticizer to obtain a slurry, or mixing a stabilizer, a plasticizer and a colorant to obtain a slurry; A plastic mixture, slurry, active magnesium hydroxide, wollastonite, a phosphorus-nitrogen flame retardant, and a dispersant are mixed to obtain a primary mixture; the mass ratio of the plastic mixture, slurry, magnesium hydroxide, wollastonite, the phosphorus-nitrogen compound flame retardant, and the dispersant is (50-65):(1-5):(20-35):(5-8):(3-7):(1-3), wherein magnesium hydroxide is a raw material for preparing active magnesium hydroxide; the phosphorus-nitrogen flame retardant is a phosphorus-nitrogen salt or a mixture of a phosphorus-nitrogen salt and polyphosphate amine; the mass ratio of the phosphorus-nitrogen salt to the polyphosphate amine is 1:2-4; The obtained primary mixture is extruded and granulated to obtain flame retardant low smoke masterbatch.

2. The preparation method according to claim 1, characterized in that The thermoplastic plastic comprises one or more of polyethylene, polypropylene, polymethyl methacrylate, ethylene-vinyl acetate copolymer, polyacrylonitrile, and polystyrene; The plasticizer is a main plasticizer, or a mixture of a main plasticizer and an auxiliary plasticizer; The main plasticizer includes one or two of a phthalate plasticizer and a phosphate plasticizer, the phthalate plasticizer includes dioctyl phthalate or dibutyl phthalate, and the phosphate plasticizer includes tricresyl phosphate; The secondary plasticizer comprises epoxidized soybean oil; The mass ratio of the thermoplastic plastic to the plasticizer is 50-60:3-10.

3. The preparation method according to claim 2, characterized in that The stabilizer comprises one or more of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; The mass ratio of the stabilizer to the plasticizer is (1-3): (1-9).

4. The preparation method according to claim 1, characterized in that The dispersant comprises an inorganic dispersant or an organic dispersant; The inorganic dispersant includes a silicate dispersant and / or an alkali metal phosphate dispersant; The organic dispersant includes one or more of triethylhexyl phosphate, cellulose derivatives, sodium lauryl sulfate and fatty acid polyethylene glycol ester.

5. The preparation method according to claim 1, 3 or 4, characterized in that: The extrusion granulation process is divided into three zones, the temperature of the first zone is 130-170°C, the temperature of the second zone is 160-190°C, and the temperature of the third zone is 140-150°C.

6. The flame retardant low smoke masterbatch obtained by the preparation method according to any one of claims 1 to 5.

7. Use of the flame-retardant low-smoke masterbatch according to claim 6 in the preparation of flame-retardant low-smoke plastic products or wires and cables.