CN113527830B - High-impact polystyrene resin composition modified by high-molecular nitrogen-halogen flame retardant and preparation method thereof - Google Patents
High-impact polystyrene resin composition modified by high-molecular nitrogen-halogen flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-smoke high-flame-retardant high impact polystyrene resin (HIPS) preparation method, firstly, vinyl amide, alkyl acryloyl halide and 1, 3-butadiene are copolymerized to have macromolecular nitrogen-halogen flame retardant with reactivity; then grafting the flame retardant to solution polymerized styrene-butadiene rubber cement (SSBR) to form a high molecular nitrogen-halogen flame retardant; secondly, carrying out amination treatment on the inorganic smoke suppressant to obtain an aminated smoke suppressant; finally, directly blending the high-molecular nitrogen-halogen flame retardant and the aminated smoke suppressant with the high-impact polystyrene resin, and granulating to prepare the high-impact polystyrene resin with the maximum smoke density of less than 110, the oxygen index of more than 41 percent and the cantilever beam notch impact strength of more than 8kJ/m 2 The low-fuming, high-flame-retardant and high-impact polystyrene resin. The method endows the HIPS resin with low smoke generation and high-efficiency flame retardance on the premise of ensuring the impact strength.
Description
Technical Field
The invention relates to a preparation method of low-smoke high-flame-retardant high-impact polystyrene resin, in particular to a preparation method of high-impact polystyrene resin modified by a high-molecular nitrogen-halogen flame retardant and a functionalized smoke suppressant.
Background
High Impact Polystyrene (HIPS) has the advantages of excellent formability, good toughness, high dimensional stability, good electrical insulation performance, easy dyeing, low moisture absorption, low price and the like, is widely applied to the industries of packaging, electronics, buildings, automobiles, household appliances, instruments, daily necessities, toys and the like, and becomes one of the fastest-developing varieties of the current general synthetic resins. However, HIPS has low oxygen index and poor flame retardant performance, so that the HIPS is difficult to meet the V-0 flame retardant standard requirement of UL94 (flammability test standard of plastic materials for instruments and parts in the United states), and is difficult to adapt to industries such as high-end electronic appliances, automobile manufacturing and the like. At present, nearly 80 percent of fire retardants used in China industry are halogen-containing fire retardants, which have the advantages of high fire-retardant efficiency, small influence on the performance of products, moderate price and efficiency/price comparable to that of other fire retardants, but have the defects of generating a large amount of smoke and toxic substances during combustion, causing difficulty in breathing of people, having more serious harm than the consequences generated by combustion and being the first risk factor of casualties caused by fire disasters. In recent years, people have higher and higher requirements on fire safety and low-smoke and flame-retardant performance of products, and research on the development of novel low-smoke and high-flame-retardant resin-burning materials has become a hotspot.
In the prior art, low smoke, high flame retardant studies on high impact polystyrene resins were made by adding inorganic flame retardants and organic flame retardants. Such as: ZL201110098731.0 discloses a magnesium hydroxide flame retardant subjected to surface treatment of sulfonated high impact polystyrene, and the flame retardant is mixed with high impact polystyrene resin to prepare a magnesium hydroxide flame retardant with the impact strength of 5.4kJ/m 2 And 29% oxygen index. CN101353461A discloses a flame-retardant high impact polystyrene compound which is prepared by compounding decahalodiphenylethane halogen flame retardant, tetrahalobisphenol A halogen flame retardant and antimony trioxide flame-retardant synergist with high impact polystyrene according to a certain proportion and performing once extrusion processing by a double-screw extruder. The composite material of organic fire retardant tetrabromobisphenol A, inorganic fire retardant hydrated magnesium oxide and antimony oxide is used to prepare simple beam with notch impact strength up to 25.3 kJ/m 2 The flame retardant property of the low-smoke flame-retardant HIPS resin reaches UL 94V-0 level (Chinese plastics, 2003,17 (8): 39-42).
The above patents and documents are basically modified by using small molecular halogen organic flame retardant and inorganic powder flame retardant, and although obvious effect has been achieved in improving flame retardancy of HIPS resin, the dosage of flame retardant is large, modification cost is high, negative influence on impact strength performance of material is large, and it is difficult to realize balance of flame retardancy and mechanical property of HIPS resin material by traditional modification methods such as mechanical stirring or surface treatment of coupling agent and active agent.
Disclosure of Invention
The invention aims to provide a high-performance high-smoke-density glass fiber reinforced plastic with the maximum smoke density of less than 110, the oxygen index of more than 41 percent and the cantilever beam notch impact strength of more than 8kJ/m 2 The preparation method of the polystyrene resin with low smoke generation, high flame retardance and high impact resistance. The invention firstly adopts vinyl amide, alkyl acrylic acyl halide and 1, 3-butadiene to copolymerize with a reactive macromolecular nitrogen-halogen flame retardant;then grafting the flame retardant to solution polymerized styrene-butadiene rubber cement (SSBR) to form a high molecular nitrogen-halogen flame retardant; secondly, carrying out amination treatment on the inorganic smoke suppressant to obtain an aminated smoke suppressant; finally, the high molecular nitrogen-halogen flame retardant, the aminated smoke suppressant and the high impact polystyrene resin are directly mixed and granulated to prepare the low-smoke high-flame-retardant high impact polystyrene resin. The method greatly improves the compatibility of the flame retardant and the smoke suppressant with High Impact Polystyrene (HIPS) resin, solves the problems of uneven dispersion, migration, precipitation and the like of the flame retardant and the smoke suppressant in the HIPS resin matrix, fully exerts the synergistic effect of the macromolecular flame retardant and the smoke suppressant, and endows the HIPS resin with low smoke generating performance and high-efficiency flame retardance on the premise of ensuring the impact strength.
The "parts" in the present invention mean parts by mass.
The preparation of the low-smoke high-flame-retardant high-impact polystyrene resin is carried out in a polymerization kettle and a screw kneading machine, and the preparation steps are as follows:
(1) Preparation of macromolecular "nitrogen-halogen" flame retardant: taking the total mass of vinyl amide and alkyl acryloyl halide as 100 parts, firstly introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 60-80 parts of vinyl amide, 20-40 parts of alkyl acryloyl halide and 0.1-0.5 part of molecular weight regulator into the polymerization kettle, stirring, mixing and heating, adding 0.05-0.2 part of initiator when the temperature of the polymerization kettle reaches 50-60 ℃, reacting for 3.0-5.0 hr, then adding 1.0-5.0 parts of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50-60min until no free monomer exists, washing and drying to obtain the macromolecular 'nitrogen-halogen' flame retardant with reaction activity.
(2) Preparation of high molecular nitrogen-halogen flame retardant: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, introducing nitrogen into a 15L stainless steel polymerization kettle for replacement for 2 to 4 times, adding 300 to 400 parts of solvent into the kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement, 0.05 to 0.5 part of molecular weight regulator and 30 to 40 parts of macromolecular nitrogen-halogen flame retardant, stirring and heating, adding 0.5 to 0.9 part of initiator when the temperature in the kettle reaches 50 to 60 ℃, reacting for 3.0 to 5.0 hours, and then adding 0.1 to 0.5 part of terminator to prepare the macromolecular nitrogen-halogen flame retardant (the grafting rate is 30 to 40%).
(3) Preparing an aminated smoke suppressant: adding 200 to 300 parts of deionized water and 10 to 20 parts of polyamine into a polymerization kettle according to 100 parts of the mass of the smoke suppressant, adjusting the pH value of the system to be 8.0 to 9.0 by using a buffering agent, adding 100 parts of the smoke suppressant and 1.0 to 5.0 parts of silane coupling agent when the temperature is raised to 70 to 80 ℃, stirring and mixing for 2.0 to 4.0 hours, and then carrying out suction filtration, washing, drying and grinding to obtain the aminated smoke suppressant.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: adding 100 parts of high impact polystyrene resin, 20 to 30 parts of high molecular nitrogen-halogen flame retardant, 5 to 10 parts of aminated smoke suppressant, 0.1 to 0.5 part of stabilizer and 0.1 to 0.5 part of antioxidant into a high-speed mixer, and mixing at a high speed for 5 to 10min, wherein the mass of the high impact polystyrene resin is 100 parts; and then directly adding the mixed materials into a screw kneading machine, reacting at 160-200 ℃ for 4-6 min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin.
The general structural formula of the high-molecular functionalized composite flame retardant is as follows:
in the formula: x is halogen element bromine and chlorine; r is C 1 ～C 4 Alkyl groups of (a); b is a small molecule segment of 1, 3-butadiene, i.e., an oligomer segment of 1, 3-butadiene; the SSBR is a solution polymerization copolymerization of 1, 3-butadiene and styrene. The alkyl acryloyl halide is one of methacryloyl bromide, ethyl acryloyl bromide, propyl acryloyl bromide, butyl acryloyl bromide, methacryloyl chloride, ethyl acryloyl chloride, propyl acryloyl chloride and butyl acryloyl chloride, and preferably methacryloyl chloride. The vinyl amide is one of acrylamide, methacrylamide, 1-butene amide, methacrylamide and 1-hexene amide, preferably acrylamideAn enamide.
The high impact polystyrene is a copolymer (HIPS) of styrene and polybutadiene rubber, can be powder or granular resin, and has Melt Flow Rate (MFR) of 0.5-20 g/10min.
The smoke inhibitor is selected from one of antimonate, zinc borate, magnesium borate, calcium metaborate and barium sulfate, and zinc borate is preferred.
The polyamine in the invention is selected from one of ethylenediamine, triethylamine, diethylenetriamine, hexamethylenetetramine and isophoronediamine, and preferably ethylenediamine.
The silane coupling agent of the present invention may be one selected from 3-glycidyloxypropyltrimethoxysilane (KH-560), N- β -aminoethyl- γ -aminopropyltrimethoxysilane (KH-602), γ -methacryloyloxypropyltrimethoxysilane (KH-570), N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane (KH-792), vinyltrimethoxysilane (A-171), preferably A-171.
The initiator of the invention is an organic peroxide selected from one of dicumyl peroxide, cumene hydroperoxide and di-tert-butyl peroxide, preferably dicumyl peroxide (DCP).
The molecular weight regulator of the present invention may be one selected from tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan, and tertiary dodecyl mercaptan is preferred.
The screw kneader according to the invention can be a single-screw extruder or a multi-screw extruder, preferably a twin-screw extruder.
The nitrogen and argon used as the displacement gas of the polymerizer in the present invention may be replaced with one of other group 0 rare gases other than radon.
The solvent, antioxidant, stabilizer, buffer and terminator used in the present invention are not particularly limited, and conventional additives commonly used in the art can be used, for example, the solvent is a hydrocarbon solvent selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene. The antioxidant is one of phenol, hindered amine and phosphite diester antioxidant. The stabilizer is stearate, such as zinc stearate or calcium stearate. The buffer of the present invention may be one selected from sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water and ammonium bicarbonate, and sodium hydroxide is preferred. The terminator is selected from one of methanol, ethanol, propanol and butanol.
The invention firstly adopts micromolecule flame retardant vinyl amide, alkyl acrylic acyl halide and 1, 3-butadiene to copolymerize with reactive macromolecule nitrogen-halogen flame retardant, which on one hand avoids the migration and precipitation of the micromolecule flame retardant in the high impact polystyrene resin matrix, enhances the synergistic effect of the micromolecule nitrogen-containing flame retardant and the halogen-containing flame retardant, improves the high efficiency and the durability of the flame retardant effect, reduces the dosage of the halogen-containing flame retardant and reduces the harm to human body and environment. On the other hand, the flame retardant has reaction activity and can be grafted to high polymer solution polymerized styrene-butadiene rubber cement (SSBR) to synthesize a high molecular nitrogen-halogen flame retardant. The macromolecular nitrogen-halogen flame retardant enables the macromolecular nitrogen-halogen flame retardant and SSBR to be an organic whole and plays two roles: on one hand, the flame retardant has the coupling effect, and mainly has a PS unit chain structure similar to that of high impact polystyrene, so that the compatibility of a macromolecular nitrogen-halogen flame retardant and the high impact polystyrene resin can be improved, the problem of uneven dispersion of the macromolecular nitrogen-halogen flame retardant in a high impact polystyrene resin adhesive matrix is effectively solved, and the HIPS resin can obtain high flame retardance. On the other hand, the flame retardant plays a toughening role, and the flame retardant mainly contains a certain amount of polybutadiene chain segments with 1,4 structures, so that the reduction of the impact resistance of HIPS resin caused by the introduction of the rigid inorganic smoke suppressant is avoided.
Secondly, the invention carries out amination treatment on the smoke suppressant through a silane coupling agent, so that the surface of the particle generates amino which can generate strong induction force and attraction with polar groups amide and acyl halide of the macromolecular nitrogen-halogen flame retardant, namely, the compatibility of the macromolecular nitrogen-halogen flame retardant and the aminated smoke suppressant can be obviously improved,the synergistic effect of the macromolecular nitrogen-halogen flame retardant and the smoke suppressant is obviously enhanced in the aspect of flame retardance, the dispersibility of the aminated smoke suppressant and the high-impact polystyrene resin can be improved, and the high efficiency and the low smoke persistence of flame retardance are improved. Therefore, the synergistic effect generated by the high-molecular nitrogen-halogen flame retardant and the aminated smoke suppressant solves the balance problem of flame retardance, smoke generating property and impact resistance of HIPS resin, endows the HIPS resin with the characteristics of low smoke generating property and high flame retardance, and can prepare the flame retardant with the maximum smoke density of less than 110, the oxygen index of more than 41 percent and the notched impact strength of a cantilever beam of more than 8kJ/m 2 The low-fuming, high-flame-retardant high impact polystyrene resin.
Firstly, raw material sources:
high impact polystyrene (HIPS, 492J), MFR:2.9g/10min, china petrochemical Yanshan petrochemical Co
Solution polymerized styrene butadiene rubber cement SSBR2564s, 10% solids content, mount petrochemical company
1, 3-butadiene, polymer grade, petrochemical company, lanzhou, china
Purity of Ethylenediamine 99%, zhengzhou chemical Co., ltd
Acrylamide, purity 99%, shandong Xuchen chemical engineering Co., ltd
Methacryloyl chloride, 99% purity, wuhanhao Rong Biotech Co., ltd
Methacryloyl bromide, 99% purity, wuhanhao Biotech limited
Fine chemical Co., ltd, jinan Taxing, with a Zinc borate particle size of 900 mesh
Vinyltrimethoxysilane (A-171), liaoning Gaizhou chemical plant
Dicumyl peroxide (DCP) half life T =133 ℃/1min, lanzhou adjuvant works
Other reagents are all commercial products
The method comprises the following steps:
determination of oxygen index: the assay was carried out as described in GB 10707-1989.
Measurement by vertical Combustion method: the assay was carried out as described in GB/T13488-1992.
Determination of the maximum smoke density: the assay was carried out as described in GB/T8323-1987.
Determination of notched Izod impact Strength: according to GB/T1843-1996.
Device and instrument for performing the following steps
Phi 34 twin-screw extruder Length/diameter =34/1 Lestreiz Germany
10L high-speed mixer Fuxin Plastic machinery plant
15L polymerizers (stirring type: two-layer three-blade inclined paddle) of Tian Hua Kouzhou Techno Co., ltd
Example 1
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: firstly, introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 2000g of pentane, 600g of acrylamide, 400g of methacryloyl chloride and 1g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 0.5g of DCP when the temperature of the polymerization kettle reaches 50 ℃, reacting for 3.0hr, adding 10g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50min, washing and drying to obtain the macromolecular nitrogen-chlorine flame retardant with the reaction activity.
(2) Preparation of high molecular nitrogen-halogen flame retardant: introducing nitrogen into a 15L stainless steel polymerization kettle for 2 times for replacement, adding 3000g of cyclohexane, 1000g of SSBR2564s, 0.5g of tert-dodecyl mercaptan and 300g of macromolecular nitrogen-chlorine flame retardant into the kettle, stirring, heating, adding 5.0g of DCP when the temperature of the polymerization kettle reaches 50 ℃, reacting for 3.0 hours, and adding 1g of methanol to prepare the high-molecular nitrogen-chlorine flame retardant (the grafting rate is 30.5%).
(3) Preparing an aminated smoke suppressant: adding 2000g of deionized water and 100g of ethylenediamine into a polymerization kettle, adjusting the pH value of the system to 8.0 by using sodium hydroxide, adding 1000g of zinc borate and 10g of A-171 when the temperature is raised to 70 ℃, stirring and mixing for 2.0 hours, and performing suction filtration, washing, drying and grinding to obtain the aminated zinc borate.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: adding 2000g of high impact polystyrene resin (492J), 400g of high molecular nitrogen-chlorine flame retardant, 100g of aminated zinc borate, 5g of calcium stearate and 3g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 5min; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: the same as in example 1.
(2) Preparation of high molecular nitrogen-halogen flame retardant: the same as in example 1.
(3) Preparing an aminated smoke suppressant: the same as in example 1.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: 2000g of high impact polystyrene resin (492J), 440g of high molecular nitrogen-chlorine flame retardant, 120g of aminated zinc borate, 6g of calcium stearate and 1010 g of antioxidant are added into a 10L high-speed mixer to be mixed for 5min at high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: firstly, introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 2 times, sequentially adding 2600g of pentane, 700g of acrylamide, 300g of methacryloyl chloride and 3g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 1.2g of DCP when the temperature of the polymerization kettle reaches 55 ℃, reacting for 4.0hr, then adding 30g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 55min, washing and drying to obtain the macromolecular nitrogen-chlorine flame retardant with the reaction activity.
(2) Preparation of high molecular nitrogen-halogen flame retardant: introducing nitrogen into a 15L stainless steel polymerization kettle for 2 times of replacement, adding 3500g of cyclohexane, 1000g of SSBR2564s, 1.5g of tert-dodecyl mercaptan and 360g of macromolecular nitrogen-chlorine flame retardant into the kettle, stirring and heating, adding 6.2g of DCP when the temperature of the polymerization kettle reaches 57 ℃, reacting for 4.0hr, and adding 3g of methanol to prepare the high-molecular nitrogen-chlorine flame retardant (the grafting rate is 36.2 percent).
(3) Preparing an aminated smoke suppressant: adding 2500g of deionized water and 140g of ethylenediamine into a polymerization kettle, adjusting the pH value of the system to 8.5 by using sodium hydroxide, adding 1000g of zinc borate and 30g of A-171 when the temperature is raised to 75 ℃, stirring and mixing for 3.0 hours, and performing suction filtration, washing, drying and grinding to obtain the aminated zinc borate.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: adding 2000g of high impact polystyrene resin (492J), 500g of high molecular nitrogen-chlorine flame retardant, 150g of aminated zinc borate, 7g of calcium stearate and 1010 5g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 7min; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 5min, and then performing extrusion, cooling and granulation to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: the same as in example 3.
(2) Preparation of high molecular nitrogen-halogen flame retardant: the same as in example 3.
(3) Preparing an aminated smoke suppressant: the same as in example 3.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: 2000g of high impact polystyrene resin (492J), 530g of high molecular nitrogen-chlorine flame retardant, 170g of aminated zinc borate, 8g of calcium stearate and 1010 6g of antioxidant are added into a 10L high-speed mixer to be mixed for 7min at high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 5min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: firstly, introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 3 times, sequentially adding 2800g of pentane, 750g of acrylamide, 250g of methacryloyl chloride and 4g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 1.7g of DCP when the temperature of the polymerization kettle reaches 57 ℃, reacting for 4.5 hours, adding 40g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 57 minutes, washing and drying to obtain the macromolecular nitrogen-chlorine flame retardant with reaction activity.
(2) Preparation of high molecular nitrogen-halogen flame retardant: after introducing nitrogen into a 15L stainless steel polymerization kettle for 3 times of replacement, 3700g of cyclohexane, 1000g of SSBR2564s, 2.0g of tert-dodecyl mercaptan and 380g of macromolecular nitrogen-chlorine flame retardant are added into the kettle, stirred and heated, 7.3g of DCP is added when the temperature of the polymerization kettle reaches 58 ℃, and after 4.0hr of reaction, 4g of methanol is added, so that the high-molecular nitrogen-chlorine flame retardant is prepared (the grafting rate is 37.9%).
(3) Preparing an aminated smoke suppressant: 2800g of deionized water and 180g of ethylenediamine are added into a polymerization kettle, the pH value of the system is adjusted to 8.8 by sodium hydroxide, 1000g of zinc borate and 45g of KH-560 are added when the temperature is increased to 79 ℃, and after stirring and mixing for 3.7 hours, the aminated zinc borate is obtained by suction filtration, washing, drying and grinding.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: 2000g of high impact polystyrene resin (492J), 570g of high molecular nitrogen-chlorine flame retardant, 180g of aminated zinc borate, 8g of calcium stearate and 1010 6g of antioxidant are added into a 10L high-speed mixer to be mixed for 8min at high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 5min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparation of macromolecular "nitrogen-bromine" flame retardant: firstly, introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 4 times, sequentially adding 2800g of hexane, 800g of acrylamide, 200g of methacryloyl bromide and 5g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 2.0g of DCP when the temperature of the polymerization kettle reaches 90 ℃, reacting for 5.0hr, adding 50g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 60min, washing and drying to obtain the macromolecular nitrogen-bromine flame retardant with the reaction activity.
(2) Preparation of high molecular nitrogen-halogen flame retardant: introducing nitrogen into a 15L stainless steel polymerization kettle for 4 times of replacement, adding 4000g of cyclohexane, 1000g of SSBR2564s, 3.0g of tert-dodecyl mercaptan and 400g of macromolecular nitrogen-bromine flame retardant into the kettle, stirring and heating, adding 9.0g of DCP when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.0hr, and adding 5g of methanol to prepare the high-molecular nitrogen-bromine flame retardant (the grafting rate is 39.8 percent).
(3) Preparing an aminated smoke suppressant: adding 3000g of deionized water and 200g of ethylenediamine into a polymerization kettle, adjusting the pH value of the system to 9.0 by using sodium hydroxide, adding 1000g of zinc borate and 50g of A-171 when the temperature is raised to 80 ℃, stirring and mixing for 4.0 hours, and performing suction filtration, washing, drying and grinding to obtain the aminated zinc borate.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: 2000g of high impact polystyrene resin (492J), 600g of high molecular nitrogen-bromine flame retardant, 200g of aminated zinc borate, 9g of calcium stearate and 1010 6g of antioxidant are added into a 10L high-speed mixer to be mixed for 10min at high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 6min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: the same as in example 1.
(2) Preparation of high molecular nitrogen-halogen flame retardant: the other conditions were the same as in example 1, except that DCP was added in an amount of 4.0g during the preparation of the polymeric "N-halo" flame retardant, namely: introducing nitrogen into a 15L stainless steel polymerization kettle for 2 times of replacement, adding 3000g of cyclohexane, 1000g of SSBR2564s, 0.5g of tert-dodecyl mercaptan and 300g of macromolecular nitrogen-chlorine flame retardant into the kettle, stirring, heating, adding 0.9g of BPO when the temperature of the polymerization kettle reaches 50 ℃, reacting for 3.0hr, and adding 1g of methanol to prepare the high-molecular nitrogen-chlorine flame retardant-1 (the grafting rate is 28.5 percent).
(3) Preparing an aminated smoke suppressant: the same as in example 1.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 1, except that the high molecular weight "nitrogen-chlorine" flame retardant was added instead of the high molecular weight "nitrogen-chlorine" flame retardant-1 in an amount of 400g in the preparation of the low smoke, high flame retardant, high impact polystyrene resin, namely: adding 2000g of high impact polystyrene resin (492J), 1 400g of high molecular nitrogen-chlorine flame retardant, 100g of aminated zinc borate, 5g of calcium stearate and 3g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 5min; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 4min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: the same as in example 2.
(2) Preparing an aminated smoke suppressant: the same as in example 2.
(3) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 2, except that the macromolecular "nitrogen-chlorine" flame retardant was not added during the preparation of the low-smoke, high-flame-retardant, high-impact polystyrene resin, but was added in an amount of 440g, i.e.: 2000g of high impact polystyrene resin (492J), 440g of macromolecular nitrogen-chlorine flame retardant, 120g of aminated zinc borate, 6g of calcium stearate and 1010 g of antioxidant are added into a 10L high-speed mixer to be mixed for 5min at high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of high molecular nitrogen-halogen flame retardant: the other conditions were the same as in example 3, except that the macromolecular "nitrogen-chlorine" flame retardant was not added during the preparation of the polymeric "nitrogen-halogen" flame retardant, but acrylamide was added in an amount of 360g, i.e.: introducing nitrogen into a 15L stainless steel polymerization kettle for 2 times of replacement, adding 3500g of cyclohexane, 1000g of SSBR2564s, 1.5g of tert-dodecyl mercaptan and 360g of acrylamide into the kettle, stirring and heating, adding 2.2g of DCP when the temperature of the polymerization kettle reaches 57 ℃, reacting for 4.0hr, and adding 3g of methanol to prepare the high-molecular acrylamide flame retardant (the grafting rate is 37.5%).
(2) Preparing an aminated smoke suppressant: the same as in example 3.
(3) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 3, except that the high molecular weight acrylamide flame retardant was added in an amount of 500g instead of the high molecular weight "nitrogen-chlorine" flame retardant in the preparation of the low smoke, high flame retardant, high impact polystyrene resin, that is: adding 2000g of high impact polystyrene resin (492J), 500g of high molecular acrylamide flame retardant, 150g of aminated zinc borate, 7g of calcium stearate and 1010 g of antioxidant into a 10L high-speed mixer for high-speed mixing for 7min; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 5min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of macromolecular nitrogen-chlorine flame retardant: the same as in example 4.
(2) Preparation of high molecular nitrogen-halogen flame retardant: the same as in example 4.
(3) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 4, except that the aminated zinc borate was not added during the preparation of the low-smoke, high-flame-retardant, high-impact polystyrene resin, but zinc borate was directly added in an amount of 170g, namely: 2000g of high impact polystyrene resin (492J), 530g of high molecular nitrogen-chlorine flame retardant, 170g of zinc borate, 8g of calcium stearate and 1010 6g of antioxidant are added into a 10L high-speed mixer to be mixed for 7min at high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 5min, and then performing extrusion, cooling and granulation to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparing an aminated smoke suppressant: the same as in example 5.
(2) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: the other conditions are the same as example 5, except that the preparation process of the low-smoke, high-flame-retardant and high-impact polystyrene resin is not added with the macromolecular nitrogen-chlorine flame retardant, but is added with the micromolecular flame retardant methacryloyl chloride, the addition amount is 570g, namely: 2000g of high impact polystyrene resin (492J), 570g of methacryloyl chloride, 180g of aminated zinc borate, 8g of calcium stearate and 1010 g of antioxidant are added into a 10L high-speed mixer to be mixed for 8min at a high speed; and finally, adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 5min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
(1) Preparation of macromolecular "nitrogen-bromine" flame retardant: the same as in example 6.
(2) Preparation of high molecular nitrogen-halogen flame retardant: the same as in example 6.
(3) Preparing an aminated smoke suppressant: the other conditions were the same as in example 6, except that instead of ethylenediamine, ethylamine was added in an amount of 200g during the preparation of the aminated smoke suppressant, i.e.: adding 3000g of deionized water and 200g of ethylamine into a polymerization kettle, adjusting the pH value of the system to 9.0 by using sodium hydroxide, adding 1000g of zinc borate and 50g of A-171 when the temperature is increased to 80 ℃, stirring and mixing for 4.0 hours, and performing suction filtration, washing, drying and grinding to obtain the aminated zinc borate-1.
(4) Preparing low-smoke high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 6, except that the aminated zinc borate was not added in the preparation of the low-smoke, high-flame-retardant, high-impact polystyrene resin, and the aminated zinc borate-1 was added in an amount of 200g, namely: adding 2000g of high impact polystyrene resin (492J), 600g of high molecular nitrogen-bromine flame retardant, 200g of aminated zinc borate-1, 9g of calcium stearate and 1010 6g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 10min; finally, adding the mixed materials into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 6min, and then performing extrusion, cooling and granulation to obtain the low-smoke high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of Low-Smoke, high-flame-retardant, high-impact polystyrene resin
| Sample numbering | Oxygen index% | Maximum smoke density | Combustion characteristic | Notched impact strength kJ/m2 of cantilever beam |
| Example 1 | 41.1 | 109 | Class V-0 | 8.3 |
| Example 2 | 41.6 | 102 | Class V-0 | 9.5 |
| Example 3 | 42.2 | 99 | Class V-0 | 10.2 |
| Example 4 | 43.5 | 95 | Class V-0 | 9.7 |
| Example 5 | 43.9 | 91 | Class V-0 | 9.3 |
| Example 6 | 44.2 | 87 | Class V-0 | 10.6 |
| Comparative example 1 | 27.5 | 196 | Not gradable | 7.2 |
| Comparative example 2 | 28.3 | 176 | Class V-1 | 6.9 |
| Comparative example 3 | 29.6 | 141 | Class V-1 | 7.2 |
| Comparative example 4 | 23.9 | 245 | Not gradable | 5.5 |
| Comparative example 5 | 22.6 | 252 | Not gradable | 5.8 |
| Comparative example 6 | 34.7 | 128 | Class V-1 | 7.9 |
| Reference sample | 18.9 | 276 | Not gradable | 6.3 |
Reference sample * : polystyrene (492J) commercially available from Yanshan petrochemical company, china petrochemical.
Claims (14)
1. A low-smoke high-flame-retardant high-impact polystyrene resin composition comprises the following components in parts by mass: 100 parts of high impact polystyrene resin; (2) 20 to 30 parts of high molecular nitrogen-halogen flame retardant; (3) 5-10 parts of aminated smoke suppressant; (4) 0.1 to 0.5 part of a stabilizer; (5) 0.1 to 0.5 part of antioxidant, which is characterized by comprising the following components in parts by weight:
the structural general formula of the high-molecular nitrogen-halogen flame retardant is as follows:
in the formula: x is bromine or chlorine, R is C 1 ～C 8 B is 1, 3-butadieneAn oligomer segment of (a); SSBR is solution polymerized styrene-butadiene rubber cement which is prepared by solution polymerization copolymerization of 1, 3-butadiene and styrene, and m and n are the number of repeating units;
the preparation method of the low-smoke high-flame-retardant high-impact polystyrene resin composition comprises the following steps:
(1) Preparation of macromolecular "nitrogen-halogen" flame retardant: taking the total mass of acrylamide and alkyl acryloyl halide as 100 parts, firstly introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 60-80 parts of acrylamide, 20-40 parts of alkyl acryloyl halide and 0.1-0.5 part of molecular weight regulator into the polymerization kettle, stirring, mixing and heating, adding 0.05-0.2 part of initiator when the temperature of the polymerization kettle reaches 50-60 ℃, reacting for 3.0-5.0 hr, then adding 1.0-5.0 parts of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50-60min until no free monomer exists, washing and drying to prepare a macromolecular 'nitrogen-halogen' flame retardant with reaction activity;
(2) Preparation of high molecular nitrogen-halogen flame retardant: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, introducing nitrogen into a 15L stainless steel polymerization kettle for replacement for 2 to 4 times, adding 300 to 400 parts of solvent into the kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement, 0.05 to 0.5 part of molecular weight regulator and 30 to 40 parts of macromolecular nitrogen-halogen flame retardant, stirring and heating, adding 0.5 to 0.9 part of initiator when the temperature in the kettle reaches 50 to 60 ℃, reacting for 3.0 to 5.0 hours, and then adding 0.1 to 0.5 part of terminator to prepare the macromolecular nitrogen-halogen flame retardant, wherein the grafting rate is 30 to 40 percent;
(3) Preparing an aminated smoke suppressant: adding 200 to 300 parts of deionized water and 10 to 20 parts of ethylenediamine into a polymerization kettle based on 100 parts of the smoke suppressant, adjusting the pH value of the system to be 8.0 to 9.0 by using a buffer, adding 100 parts of the smoke suppressant and 1.0 to 5.0 parts of a silane coupling agent when the temperature is raised to 70 to 80 ℃, stirring and mixing for 2.0 to 4.0 hours, and then carrying out suction filtration, washing, drying and grinding to obtain the aminated smoke suppressant;
(4) Preparation of low-smoke, high-flame-retardant and high-impact polystyrene resin composition: adding 100 parts of high impact polystyrene resin, 20 to 30 parts of high molecular nitrogen-halogen flame retardant, 5 to 10 parts of aminated smoke suppressant, 0.1 to 0.5 part of stabilizer and 0.1 to 0.5 part of antioxidant into a high-speed mixer, and mixing at a high speed for 5 to 10min, wherein the mass of the high impact polystyrene resin is 100 parts; and then directly adding the mixed materials into a screw kneading machine, reacting at the temperature of 160-200 ℃ for 4-6 min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin composition.
2. A low smoke, high flame retardant high impact polystyrene resin composition as claimed in claim 1 wherein said high impact polystyrene resin is a copolymer of styrene and polybutadiene rubber and has a melt flow rate of 0.5-20 g/10min.
3. The low smoke, high flame retardant, high impact polystyrene resin composition of claim 1, wherein said alkyl acryloyl halide is one of methacryloyl bromide, ethylacryloyl bromide, propylacryloyl bromide, butylacryloyl bromide, methacryloyl chloride, ethylacryloyl chloride, propylacryloyl chloride, butylacryloyl chloride.
4. The low smoke, high flame retardant high impact polystyrene resin composition of claim 3, wherein said alkyl acryloyl halide is methacryloyl chloride.
5. A low smoke, high flame retardant high impact polystyrene resin composition as claimed in claim 1 wherein said molecular weight modifier is selected from one of tertiary deca-mercaptan, tertiary dodeca-mercaptan, tertiary tetradecane-mercaptan, and tertiary hexadecane-mercaptan.
6. The low-smoke, high-flame-retardant, high-impact polystyrene resin composition of claim 1, wherein said molecular weight modifier is t-dodecyl mercaptan.
7. The low-smoke, high-flame-retardant high-impact polystyrene resin composition of claim 1, wherein said initiator is selected from one of dicumyl peroxide, cumene hydroperoxide and di-t-butyl peroxide.
8. The low smoke, high flame retardant, high impact polystyrene resin composition of claim 7, wherein said initiator is dicumyl peroxide.
9. The low smoke, high flame retardant high impact polystyrene resin composition of claim 1 wherein said silane coupling agent is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, and vinyltrimethoxysilane.
10. The low-smoke, high-flame-retardant high-impact polystyrene resin composition of claim 1, wherein said silane coupling agent is vinyltrimethoxysilane.
11. The low smoke, high flame retardant, high impact polystyrene resin composition of claim 1 wherein said smoke suppressant is selected from one of the group consisting of antimonates, zinc borate, magnesium borate, calcium metaborate and barium sulfate.
12. A low smoke, high flame retardant, high impact polystyrene resin composition as claimed in claim 11 wherein said smoke suppressant is zinc borate.
13. A method of preparing a low smoke, high flame retardant, high impact polystyrene resin composition as claimed in any one of claims 1 to 12, characterized in that the preparation process is:
(1) Preparation of macromolecular "nitrogen-halogen" flame retardant: taking the total mass of acrylamide and alkyl acryloyl halide as 100 parts, firstly introducing nitrogen into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 60-80 parts of acrylamide, 20-40 parts of alkyl acryloyl halide and 0.1-0.5 part of molecular weight regulator into the polymerization kettle, stirring, mixing and heating, adding 0.05-0.2 part of initiator when the temperature of the polymerization kettle reaches 50-60 ℃, reacting for 3.0-5.0 hr, then adding 1.0-5.0 parts of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50-60min until no free monomer exists, washing and drying to prepare a macromolecular 'nitrogen-halogen' flame retardant with reaction activity;
(2) Preparation of high molecular nitrogen-halogen flame retardant: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, introducing nitrogen into a 15L stainless steel polymerization kettle for replacement for 2 to 4 times, adding 300 to 400 parts of solvent into the kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement, 0.05 to 0.5 part of molecular weight regulator and 30 to 40 parts of macromolecular nitrogen-halogen flame retardant, stirring and heating, adding 0.5 to 0.9 part of initiator when the temperature in the kettle reaches 50 to 60 ℃, reacting for 3.0 to 5.0 hours, and then adding 0.1 to 0.5 part of terminator to prepare the macromolecular nitrogen-halogen flame retardant, wherein the grafting rate is 30 to 40 percent;
(3) Preparing an aminated smoke suppressant: adding 200 to 300 parts of deionized water and 10 to 20 parts of ethylenediamine into a polymerization kettle based on 100 parts of the smoke suppressant, adjusting the pH value of the system to be 8.0 to 9.0 by using a buffer, adding 100 parts of the smoke suppressant and 1.0 to 5.0 parts of a silane coupling agent when the temperature is raised to 70 to 80 ℃, stirring and mixing for 2.0 to 4.0 hours, and then carrying out suction filtration, washing, drying and grinding to obtain the aminated smoke suppressant;
(4) Preparation of low-smoke, high-flame-retardant and high-impact polystyrene resin composition: adding 100 parts of high impact polystyrene resin, 20 to 30 parts of high molecular nitrogen-halogen flame retardant, 5 to 10 parts of aminated smoke suppressant, 0.1 to 0.5 part of stabilizer and 0.1 to 0.5 part of antioxidant into a high-speed mixer, and mixing at high speed for 5 to 10min, wherein the mass of the high impact polystyrene resin is 100 parts; and then directly adding the mixed materials into a screw kneading machine, reacting at the temperature of 160-200 ℃ for 4-6 min, extruding, cooling and granulating to obtain the low-smoke high-flame-retardant high-impact polystyrene resin composition.
14. The method for preparing a highly flame retardant, low smoke, high impact polystyrene resin composition as claimed in claim 13, wherein said screw kneader is a twin-screw extruder.
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