阅读说明：本技术 阻燃剂及阻燃pc塑料 (Flame retardant and flame-retardant PC plastic ) 是由 张燕丹 于 2020-07-10 设计创作，主要内容包括：本发明公开了一种阻燃剂及阻燃PC塑料,所述阻燃剂包括以下原料：氨基噻唑类化合物、三亚乙基二胺、烯基卤硅烷类化合物、四氢呋喃、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与偶氮二异丁酸二甲酯,本发明制备的阻燃剂及PC塑料具有良好的阻燃性能。(The invention discloses a flame retardant and flame-retardant PC plastic, wherein the flame retardant comprises the following raw materials: aminothiazole compounds, triethylene diamine, alkenyl halogen silane compounds, tetrahydrofuran, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dimethyl azodiisobutyrate.)

1. The preparation method of the flame retardant is characterized by comprising the following steps:

the method comprises the following steps: mixing aminothiazole compounds and triethylene diamine, adding a functionalized solution, reacting at 28-58 ℃ for 5-10h, filtering, concentrating under reduced pressure, and drying to obtain a product W; the functionalized solution is a mixture of alkenyl halogen silane compounds and tetrahydrofuran according to the mass ratio of (1-5) to (35-50);

step two: adding the product W of the first step and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into toluene, and stirring; adding a toluene solution of dimethyl azodiisobutyrate, carrying out reflux reaction at 75-95 ℃ for 20-30h, cooling to room temperature, filtering and collecting a crude product, washing and drying to obtain the flame retardant.

2. The method of preparing a flame retardant of claim 1, comprising the steps of:

the method comprises the following steps: mixing an aminothiazole compound and triethylene diamine under the protection of nitrogen, wherein the mass ratio of the aminothiazole compound to the triethylene diamine is (5-10) to (1-5); adding the functionalized solution at the speed of 0.5-2mL/min, reacting for 5-10h at the temperature of 28-58 ℃, wherein the stirring speed is 100-300rpm, and the mass ratio of the functionalized solution to the aminothiazole compound is 40: (1-10); filtering, collecting filtrate, concentrating under reduced pressure, and drying at 70-90 deg.C for 5-20h to obtain product W; the functionalized solution is a mixture of alkenyl halogen silane compounds and tetrahydrofuran according to the mass ratio of (1-5) to (35-50);

step two: under the protection of nitrogen, adding the product W and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide obtained in the step one into toluene, and stirring at the temperature of 50-100 ℃ for 5-20min at the stirring speed of 100-500rpm, wherein the mass ratio of the product W, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the toluene is (3-7) to (1-5) to (25-35); adding a toluene solution of dimethyl azodiisobutyrate at the rate of 0.5-2.5mL/min, and carrying out reflux reaction at the temperature of 75-95 ℃ for 20-30h, wherein the stirring rate is 100-500rpm, the mass ratio of the toluene solution of dimethyl azodiisobutyrate to the product W is (10-15): 5-10, and the mass ratio of the toluene solution of dimethyl azodiisobutyrate to toluene is (0.01-0.1): 13; cooling to room temperature, filtering and collecting a crude product, washing with toluene for 1-5 times, and drying at 60-80 ℃ for 25-35h to obtain the flame retardant.

3. The process for preparing a flame retardant according to claim 2, comprising the steps of:

the method comprises the following steps: mixing an aminothiazole compound and triethylene diamine under the protection of nitrogen, wherein the mass ratio of the aminothiazole compound to the triethylene diamine is (5-10) to (1-5); adding the functionalized solution at the speed of 0.5-2mL/min, reacting for 5-10h at the temperature of 28-58 ℃, wherein the stirring speed is 100-300rpm, and the mass ratio of the functionalized solution to the aminothiazole compound is 40: (1-10); filtering, collecting filtrate, concentrating under reduced pressure, and drying at 70-90 deg.C for 5-20h to obtain product W; the functionalized solution is a mixture of alkenyl halogen silane compounds and tetrahydrofuran according to the mass ratio of (1-5) to (35-50);

step two: under the protection of nitrogen, adding the product W and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide obtained in the step one into toluene, and stirring at the temperature of 50-100 ℃ for 5-20min at the stirring speed of 100-500rpm, wherein the mass ratio of the product W, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the toluene is (3-7) to (1-5) to (25-35); adding a toluene solution of dimethyl azodiisobutyrate at the rate of 0.5-2.5mL/min, adding a modifier, carrying out reflux reaction at the temperature of 75-95 ℃ for 20-30h, wherein the stirring rate is 100-500rpm, the mass ratio of the toluene solution of dimethyl azodiisobutyrate to a product W is (10-15): 5-10), the mass ratio of the toluene solution of dimethyl azodiisobutyrate to toluene is (0.01-0.1):13, and the mass ratio of the modifier to the product W is (0.1-1): 5-10); cooling to room temperature, filtering and collecting a crude product, washing with toluene for 1-5 times, and drying at 60-80 ℃ for 25-35h to obtain the flame retardant.

4. The method of preparing the flame retardant according to any one of claims 1 to 3, wherein the aminothiazole compound is at least one of 2-aminothiazole-5-sulfonamide, ethyl 2- (2-aminothiazole-4-yl) glyoxylate and 6-methoxy-2-aminobenzothiazole.

5. The method for producing a flame retardant according to any one of claims 1 to 3, wherein the alkenyl halosilane-based compound is allyldimethylchlorosilane and/or vinyldimethylfluorosilane.

6. The flame retardant is characterized by comprising the following raw materials: aminothiazoles, triethylenediamine, alkenylhalosilanes, tetrahydrofuran, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dimethyl azodiisobutyrate.

7. The flame retardant of claim 6, prepared by the method of any one of claims 1-5.

8. Use of the flame retardant according to claim 6 or 7 in PC plastics, PA plastics, ABS plastics, PET plastics.

9. The flame-retardant PC plastic is characterized by comprising the following raw materials: 80-100 parts by weight of PC, 1-10 parts by weight of the flame retardant of claim 7, 0.1-0.5 part by weight of antioxidant 626 and 0.1-2 parts by weight of stearic acid.

Technical Field

The invention relates to the field of plastics, and particularly relates to a flame retardant and a flame-retardant PC plastic.

Background

Engineering plastics are generally classified into general engineering plastics and special engineering plastics. Common general engineering plastics include polyamide, polycarbonate, polyformaldehyde, modified polyphenyl ether and the like; the special engineering plastics mainly comprise polyimide, polyphenylene sulfide, aromatic polyamide, polyarylate, polyphenyl ester, fluororesin and the like. The engineering plastic has the advantages of excellent comprehensive performance, good heat resistance and cold resistance, excellent mechanical performance in a wide temperature range, good corrosion resistance, less environmental influence, good durability, easy processing, high production efficiency and cost saving. However, the engineering plastics are poor in flame retardant property and easy to burn, and fire disasters are caused in the using process, so that the life health and property safety are seriously threatened. Therefore, the development of high-quality flame retardant for engineering plastics is very important for improving the flame retardant performance while ensuring the excellent comprehensive performance of the engineering plastics.

The common flame retardant comprises a halogen flame retardant, an inorganic flame retardant, an organic flame retardant and the like, and the flame retardants have respective advantages and disadvantages, and often have more addition amount in the use process, which can cause the reduction of the performance of the engineering plastics, such as mechanical property, light transmittance, heat resistance and cold resistance.

Disclosure of Invention

In view of the defects of the prior art, the invention adopts the following specific technical scheme: provides a flame retardant and a flame-retardant PC plastic.

A flame retardant comprises the following raw materials: aminothiazoles, triethylenediamine, alkenylhalosilanes, tetrahydrofuran, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dimethyl azodiisobutyrate.

Preferably, the flame retardant comprises the following raw materials: aminothiazole compounds, triethylene diamine, alkenyl halogen silane compounds, tetrahydrofuran, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a modifier and dimethyl azodiisobutyrate.

The invention constructs a new nitrogen-silicon-phosphorus synergistic flame-retardant composite system by using three main raw materials of aminothiazole compounds (nitrogen supply system), alkenyl halogen silane compounds (silicon supply system) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (phosphorus supply system) to react with each other; in the process of burning the base material, the nitrogenous group in the flame retardant can absorb a large amount of heat when heated and decomposed, and simultaneously releases non-combustible gas, so that the surface temperature of the base material and the concentration of the combustible gas are reduced, and the flame retardant plays a role in gas-phase flame retardance; the silicon-containing groups in the flame retardant are heated and melted, migrate to the surface of the material and are matched with matrix carbon residue to form a stable and compact covering layer to prevent heat and oxygen exchange and wrap gas released during the combustion of the material, and when the gas is continuously increased, the gas breaks through the carbon layer and is rapidly sprayed out to extinguish residual flame on the surface of the material and prevent the material from continuing to combust, so that the flame retardant effect is exerted in a condensed phase; the biphenyl and phosphaphenanthrene structures contained in the phosphorus supply system of the flame retardant enable the thermal stability and the chemical stability of the flame retardant to be better, and the phosphorus supply system can decompose and release phosphorus-containing free radicals when a base material burns, plays a role in gas-phase flame retardance, quenches active free radicals such as hydroxyl free radicals and hydrogen free radicals in combustion reaction, can decompose and generate phosphoric acid strong acid, plays a role in a condensed phase, promotes the carbonization process of the base material, and forms a carbon layer; the three are in mutual cooperation and indispensable in the flame-retardant process and play a role together.

It has further been found that the use of the flame retardant brings about another technical problem that the mechanical properties are remarkably reduced, and although the flame retardant property of the base material is enhanced by the use of the flame retardant, the impact resistance of the base material is reduced to some extent. In order to solve the technical problems, the invention modifies the flame retardant by using a modifier; on one hand, the modifier introduces active epoxy groups into the flame-retardant composite system, provides a large number of crosslinking sites for the matrix material, and is matched with a silicon-oxygen-silicon structure to form a three-dimensional network structure, so that a large amount of energy brought by the action of external force can be absorbed; on the other hand, the modifier also introduces flexible branched chain structures of different levels into the flame-retardant composite system, can buffer external force impact for the matrix material, and improves the molecular chain movement capacity in the matrix material, thereby overcoming the defect of reduced impact resistance caused by adding a flame retardant. In addition, 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyl trimethoxy silane are compounded to serve as modifiers to modify the flame retardant, so that synergistic effect is achieved, and the impact resistance is further improved; the 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyltrimethoxysilane are compounded to provide cross-linking sites in different forms for a base material, and a three-dimensional network structure formed by the mutual matching of the cross-linking sites and a silicon-oxygen-silicon structure is more compact and more beneficial to absorbing energy brought by external force; meanwhile, 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyl trimethoxy silane are compounded into a flame retardant, so that a richer flexible branched chain structure is introduced, the external impact buffering effect is better, and the impact resistance of the base material can be more effectively improved.

Preferably, the flame retardant is prepared by the following method:

the method comprises the following steps: mixing aminothiazole compounds and triethylene diamine, adding a functionalized solution, reacting at 28-58 ℃ for 5-10h, filtering, concentrating under reduced pressure, and drying to obtain a product W;

step two: adding the product W of the first step and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into toluene, and stirring; adding a toluene solution of dimethyl azodiisobutyrate, adding a modifier, carrying out reflux reaction at 75-95 ℃ for 20-30h, cooling to room temperature, filtering, collecting a crude product, washing, and drying to obtain the flame retardant.

Preferably, the flame retardant is prepared by the following method:

the method comprises the following steps: mixing an aminothiazole compound and triethylene diamine under the protection of nitrogen, wherein the mass ratio of the aminothiazole compound to the triethylene diamine is (5-10) to (1-5); adding the functionalized solution at the speed of 0.5-2mL/min, reacting for 5-10h at the temperature of 28-58 ℃, wherein the stirring speed is 100-300rpm, and the mass ratio of the functionalized solution to the aminothiazole compound is 40: (1-10); filtering, collecting filtrate, concentrating under reduced pressure, and drying at 70-90 deg.C for 5-20h to obtain product W; the functionalized solution is a mixture of alkenyl halogen silane compounds and tetrahydrofuran according to the mass ratio of (1-5) to (35-50);

step two: under the protection of nitrogen, adding the product W and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide obtained in the step one into toluene, and stirring at the temperature of 50-100 ℃ for 5-20min at the stirring speed of 100-500rpm, wherein the mass ratio of the product W, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the toluene is (3-7) to (1-5) to (25-35); adding a toluene solution of dimethyl azodiisobutyrate at the rate of 0.5-2.5mL/min, adding a modifier, carrying out reflux reaction at the temperature of 75-95 ℃ for 20-30h, wherein the stirring rate is 100-500rpm, the mass ratio of the toluene solution of dimethyl azodiisobutyrate to a product W is (10-15): 5-10), the mass ratio of the toluene solution of dimethyl azodiisobutyrate to toluene is (0.01-0.1):13, and the mass ratio of the modifier to the product W is (0.1-1): 5-10); cooling to room temperature, filtering, collecting crude product, washing with toluene for 1-5 times, and drying at 60-80 deg.C for 25-35h to obtain flame retardant.

Preferably, the aminothiazole compound is at least one of 2-aminothiazole-5-sulfonamide, 2- (2-aminothiazole-4-yl) ethyl glyoxylate and 6-methoxy-2-aminobenzothiazole; further preferably, the aminothiazole compound is a mixture of 6-methoxy-2-aminobenzothiazole and 2-aminothiazole-5-sulfonamide according to the mass ratio of 1 (1-5).

Preferably, the alkenyl halogen silane compound is allyl dimethyl chlorosilane and/or vinyl dimethyl fluorosilane; further preferably, the allyl dimethylchlorosilane is allyl dimethylchlorosilane.

Preferably, the modifier is 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and/or 3-glycidyl oxypropyl trimethoxy silicon, and further preferably, the modifier is a mixture of 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyl trimethoxy silane in a mass ratio of (1-3): 1.

Preferably, the flame retardant is applied to PC plastics, PA plastics, ABS plastics and PET plastics.

The invention also provides flame-retardant PC plastic which comprises the following raw materials: 80-100 parts of PC, 1-10 parts of the flame retardant, 0.1-0.5 part of antioxidant 626 and 0.1-2 parts of stearic acid.

The invention also provides flame-retardant PC plastic which is prepared by the following method: mixing 80-100 parts by weight of PC, 1-10 parts by weight of the flame retardant, 0.1-0.5 part by weight of the antioxidant 626 and 0.1-2 parts by weight of stearic acid, extruding and granulating, wherein the temperature of a feeding section is set to be 250-260 ℃, the temperature of a melting section is set to be 260-265 ℃, the temperature of a homogenizing section is set to be 265-270 ℃, and the temperature of a nose is set to be 270-280 ℃; drying the extruded granules at 80-100 ℃ for 10-24h, and then performing injection molding at the temperature of 250-260 ℃ in the I region, 260-270 ℃ in the II region and 250-260 ℃ in the III region.

The invention has the beneficial effects that: the flame retardant prepared by the method can obviously improve the flame retardant property of the base material. The invention constructs a new nitrogen-silicon-phosphorus synergistic flame-retardant composite system by using three main raw materials of aminothiazole compounds (nitrogen supply system), alkenyl halogen silane compounds (silicon supply system) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (phosphorus supply system) to react with each other; in the process of burning the base material, the nitrogenous group in the flame retardant can absorb a large amount of heat when heated and decomposed, and simultaneously releases non-combustible gas, so that the surface temperature of the base material and the concentration of the combustible gas are reduced, and the flame retardant plays a role in gas-phase flame retardance; the silicon-containing groups in the flame retardant are heated and melted, migrate to the surface of the material and are matched with matrix carbon residue to form a stable and compact covering layer to prevent heat and oxygen exchange and wrap gas released during the combustion of the material, and when the gas is continuously increased, the gas breaks through the carbon layer and is rapidly sprayed out to extinguish residual flame on the surface of the material and prevent the material from continuing to combust, so that the flame retardant effect is exerted in a condensed phase; the biphenyl and phosphaphenanthrene structures contained in the phosphorus supply system of the flame retardant enable the thermal stability and the chemical stability of the flame retardant to be better, and the phosphorus supply system can decompose and release phosphorus-containing free radicals when a base material burns, plays a role in gas-phase flame retardance, quenches active free radicals such as hydroxyl free radicals and hydrogen free radicals in combustion reaction, can decompose and generate phosphoric acid strong acid, plays a role in a condensed phase, promotes the carbonization process of the base material, and forms a carbon layer; the three are in mutual cooperation and indispensable in the flame-retardant process and play a role together.

Further, the flame retardant is modified by a modifier; on one hand, the modifier introduces active epoxy groups into the flame-retardant composite system, provides a large number of crosslinking sites for the matrix material, and is matched with a silicon-oxygen-silicon structure to form a three-dimensional network structure, so that a large amount of energy brought by the action of external force can be absorbed; on the other hand, the modifier also introduces flexible branched chain structures of different levels into the flame-retardant composite system, can buffer external force impact for the matrix material, and improves the molecular chain movement capacity in the matrix material, thereby overcoming the defect of reduced impact resistance caused by adding a flame retardant. When 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyl trimethoxy silane are compounded to be used as a modifier to modify a flame retardant, the synergistic effect is realized, and the impact resistance can be further improved; the 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyltrimethoxysilane are compounded to provide cross-linking sites in different forms for a base material, and a three-dimensional network structure formed by the mutual matching of the cross-linking sites and a silicon-oxygen-silicon structure is more compact and more beneficial to absorbing energy brought by external force; meanwhile, 1, 5-bis (glycidyl ether propyl) 3-phenyl-1, 1,3,5, 5-pentamethyl trisiloxane and 3-glycidyl oxypropyl trimethoxy silane are compounded into a flame retardant, so that a richer flexible branched chain structure is introduced, the external impact buffering effect is better, and the impact resistance of the base material can be more effectively improved.

Detailed Description

The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.