CN113444333B - Preparation method of environment-friendly low-smoke flame-retardant high-impact polystyrene - Google Patents

Preparation method of environment-friendly low-smoke flame-retardant high-impact polystyrene Download PDF

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CN113444333B
CN113444333B CN202110794349.7A CN202110794349A CN113444333B CN 113444333 B CN113444333 B CN 113444333B CN 202110794349 A CN202110794349 A CN 202110794349A CN 113444333 B CN113444333 B CN 113444333B
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smoke
impact polystyrene
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flame
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CN113444333A (en
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朱博源
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Shanghai Gelan Chemical Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention provides a preparation method of environment-friendly low-smoke flame-retardant high-impact polystyrene resin. Firstly, synthesizing a macromolecular phosphorus-nitrogen flame retardant by using a micromolecular flame retardant allyl phosphate diester and methacrylamide; secondly, carrying out grafting reaction on the solution polymerized styrene-butadiene rubber cement through allyl phosphodiester to prepare grafted solution polymerized styrene-butadiene rubber cement, and coating two alcohol-esterified compound smoke suppressants to prepare a functional compound smoke suppressive agent; finally, directly blending and granulating the macromolecular phosphorus-nitrogen flame retardant, the functional composite smoke suppressant and the high impact polystyrene resin to prepare the high impact polystyrene resin with the maximum smoke density of less than 80, the oxygen index of more than 42 percent and the notched impact strength of a cantilever beam of more than 10kJ/m 2 The environment-friendly low-smoke flame-retardant high impact polystyrene resin. The method has the characteristics of environmental protection, good smoke suppression efficiency, high flame retardant efficiency, low modification cost and the like.

Description

Preparation method of environment-friendly low-smoke flame-retardant high-impact polystyrene
Technical Field
The invention relates to a preparation method of environment-friendly low-smoke flame-retardant high-impact polystyrene resin, in particular to a preparation method of high-impact polystyrene resin modified by a macromolecular phosphorus-nitrogen flame retardant and a functionalized composite 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, the HIPS main chain contains a large amount of elements such as carbon, hydrogen and the like which are easy to combust with oxygen at high temperature, so that the HIPS main chain has low oxygen index and poor flame retardant property, is difficult to meet the V-0 flame retardant standard requirement of UL94 (flammability test standard of plastic materials for American instruments and parts), and is difficult to adapt to industries such as high-end electronic appliances, automobile manufacturing and the like. At present, with the increasing enhancement of global safety and environmental protection consciousness, people have higher and higher requirements on fire safety and flame retardant property of products, and the application of the traditional halogen-containing flame retardant is increasingly limited due to self corrosivity and toxicity of combustion products. Therefore, the development of the halogen-free flame retardant which is environment-friendly, nontoxic and harmless becomes a research hotspot in the field of plastic modification.
In the prior art, the research on halogen-free flame retardant of high impact polystyrene resin is mainly prepared by adding inorganic and organic halogen-free flame retardants. Such as: ZL96116942.7 discloses an environment-friendly flame-retardant rubber floor with low smoke, low toxicity and good flame-retardant property, which is prepared by mutually matching and using halogen-free flame retardant aluminum (magnesium) hydroxide, antimony trioxide and phosphorus flame retardant through a mixing and blending process. ZL201110098731.0 discloses a magnesium hydroxide flame retardant subjected to surface treatment of sulfonated high impact polystyrene, which is mixed with high impact polystyrene resin to prepare a magnesium hydroxide flame retardant with impact strength of 5.4kJ/m 2 And the oxygen index is 29 percent. CN201910089719.X discloses a flame retardant micro-foaming polyphenylene oxide composite material prepared from an organic phosphorus flame retardant, inorganic hypophosphite, polyphenylene oxide and high impact polystyrene through a mixing and blending process.
The patents adopt small-molecular organic and inorganic powder halogen-free flame retardants for modification, and although obvious effects are obtained on improving the flame retardance of HIPS resin, the halogen-free flame retardants and the HIPS resin have far different surface properties, different interfacial functions, large flame retardant consumption, high modification cost, unstable product quality and other problems.
Disclosure of Invention
The invention aims to provide a high-performance composite material with the maximum smoke density of less than 80, the oxygen index of more than 42 percent and the cantilever beam notch impact strength of more than 10kJ/m 2 The preparation method of the environment-friendly low-smoke flame-retardant high impact polystyrene resin. Firstly, synthesizing a macromolecular phosphorus-nitrogen flame retardant by using a micromolecular flame retardant allyl phosphate diester and methacrylamide; secondly, the allyl phosphate diester is used for carrying out grafting reaction on the solution polymerized styrene-butadiene rubber cement to prepare grafted solution polymerized styrene-butadiene rubber cement, then the inorganic composite smoke suppressant is carried out alcohol esterification treatment, and then the grafted solution polymerized styrene-butadiene rubber cement is used for carrying out alcohol esterification on the smoke suppressantCoating to obtain a functional composite smoke suppressant; and finally, directly blending and granulating the macromolecular phosphorus-nitrogen flame retardant, the functional composite smoke suppressant and the high impact polystyrene resin to prepare the environment-friendly low-smoke flame-retardant high impact polystyrene resin. The method realizes the macro-molecular of the flame retardant, greatly improves the compatibility of the flame retardant and the smoke suppressant with High Impact Polystyrene (HIPS) resin, avoids the damage of the smoke suppressant to the mechanical property of the HIPS resin, fully exerts the synergistic effect of the macromolecular flame retardant and the smoke suppressant, and endows the HIPS resin with the characteristics of environmental protection, low smoke generation, high flame retardance and durability on the premise of ensuring the impact strength.
The "parts" in the present invention mean parts by mass.
The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin is carried out in a reaction kettle and a screw kneading machine, and the preparation steps are as follows:
(1) Preparing a functional smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, firstly introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 to 4 times, sequentially adding 200 to 300 parts of solvent, 100 parts of solution-polymerized styrene-butadiene rubber cement and 20 to 30 parts of allyl phosphate diester into a polymerization kettle, adding 0.1 to 0.5 part of initiator when the temperature is raised to 60 to 80 ℃, stirring for reaction for 6.0 to 8.0 hours, and then adding 1.0 to 5.0 parts of terminator to prepare the graft solution-polymerized styrene-butadiene rubber cement (the grafting ratio is 5.0 to 10.0 percent).
b, preparing a functional smoke suppressant: adding 200 to 300 parts of solvent, 5 to 10 parts of polyol laurate and 1.0 to 3.0 parts of silane coupling agent into a polymerization kettle according to 100 parts of the total mass of the smoke suppressant, adjusting the pH value of the system to be 9.0 to 10.0 by using a buffering agent, adding 60 to 80 parts of smoke suppressant 1 and 20 to 40 parts of smoke suppressant 2 when the temperature is raised to 70 to 80 ℃, stirring and mixing for 2.0 to 4.0 hours, then adding 30 to 40 parts of graft solution-polymerized styrene-butadiene rubber cement, stirring and mixing for 4.0 to 6.0 hours, washing, drying and grinding to obtain the functional composite smoke suppressant.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: taking the total mass of the reactive flame retardant as 100 parts, firstly introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 to 4 times, sequentially adding 200 to 300 parts of solvent, 60 to 70 parts of allyl phosphate diester, 30 to 40 parts of methacrylamide and 0.1 to 0.5 part of molecular weight regulator into a polymerization kettle, stirring, mixing and heating, adding 0.05 to 0.3 part of initiator when the temperature of the polymerization kettle reaches 50 to 70 ℃, reacting for 4.0 to 7.0 hours, and washing and drying after the reaction is finished to obtain the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin: taking 100 parts of high impact polystyrene resin as a base material, adding 100 parts of the high impact polystyrene resin, 10 to 20 parts of macromolecular phosphorus-nitrogen flame retardant, 5 to 10 parts of functionalized composite smoke suppressant, 0.2 to 0.6 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; 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 environment-friendly low-smoke flame-retardant high-impact polystyrene resin.
The macromolecular phosphorus-nitrogen flame retardant has the following structural general formula:
Figure 38704DEST_PATH_IMAGE001
in the formula: r is C 1 ～C 8 Alkyl group of (1). The allyl phosphate diester is one of dimethyl allyl phosphate, diethyl allyl phosphate, dipropyl allyl phosphate, dibutyl allyl phosphate, dipentyl allyl phosphate, dihexyl allyl phosphate, diheptyl allyl phosphate and dioctyl allyl phosphate, and preferably diethyl allyl phosphate.
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 solution polymerized styrene-butadiene rubber cement is prepared by the solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound. Wherein the solid content of the solution polymerized styrene-butadiene rubber cement is 5-20 w%.
The smoke suppressant 1 of the present invention is selected from magnesium hydroxide [ Mg (OH) 2 ]Aluminum hydroxide [ Al (OH) 3 ]Calcium hydroxide, hydrotalcite [ Mg 6 Al 2 (OH) 16 CO 3 ·4H 2 O]Calcium aluminate [3 CaO. Al 2 O 3 ·6H 2 O]Calcium carbonate, preferably aluminum hydroxide.
The smoke suppressant 2 is an inorganic hypophosphite selected from zinc hypophosphite, aluminum hypophosphite, calcium hypophosphite and magnesium hypophosphite, and preferably the aluminum hypophosphite.
The lauric acid polyol ester is selected from one or more of ethylene glycol laurate, propylene glycol laurate, glycerol laurate, butylene glycol laurate and pentaerythritol laurate.
The initiator is an organic peroxide selected from dicumyl peroxide, cumene hydroperoxide, benzoyl Peroxide (BPO) and di-tert-butyl peroxide, and the Benzoyl Peroxide (BPO) is preferred.
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 silane coupling agent can be selected from one of 3-glycidyloxypropyltrimethoxysilane (KH-560), N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane (KH-602), gamma-methacryloyloxypropyltrimethoxysilane (KH-570), N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792) and vinyltrimethoxysilane (A-171), preferably KH-560.
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, terminating agent and buffering agent 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. The stabilizer is stearate, such as zinc stearate or calcium stearate. The terminator can be one or more selected from diethylhydroxylamine, hydroxylamine sulfate and sodium fermet. The buffer may be one selected from sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water, ammonium bicarbonate, preferably sodium hydroxide.
The invention firstly uses the silane coupling agent and the lauric acid polyol ester to carry out alcohol esterification treatment on the surfaces of inorganic hypophosphite and aluminum hydroxide of two smoke inhibitors, so that the surfaces of inorganic particles are provided with ester groups and hydroxyl groups, and in addition, the solution polymerized styrene-butadiene rubber cement is grafted by adopting the allyl diethyl phosphate, so that the mutual attraction with the surfaces of the inorganic smoke inhibitors can be obviously enhanced, the caking property between the smoke inhibitors and the solution polymerized styrene-butadiene rubber cement is improved, and a compact coating layer of the solution polymerized styrene-butadiene rubber cement is formed on the surface of the smoke inhibitor, thereby preparing the functional composite smoke inhibitor. The functional composite smoke suppressant mainly plays two roles: on one hand, the coating layer contains a styrene chain segment which is similar to the structure of the high impact polystyrene and also contains a polar group ester group which is the same as the macromolecular phosphorus-nitrogen flame retardant, so that the synergistic effect of the two smoke suppressants on the smoke suppression effect and the synergistic effect of the functional composite smoke suppressor and the macromolecular phosphorus-nitrogen flame retardant on the flame retardation are obviously enhanced, the synergistic effect of the two aspects promotes the HIPS resin to be quickly carbonized on the surface during combustion, the structure of the carbon layer is compact and hard, and the heat and gas blocking effect is better played. On the other hand, the coating layer plays a toughening role, which is mainly because the coating layer contains a certain amount of polybutadiene chain segments with 1,4 structures, and the reduction of the impact resistance of the HIPS resin caused by the introduction of the rigid inorganic smoke inhibitor is avoided. And secondly, the halogen-free flame retardant is used, so that the harm of a large amount of corrosive and toxic smoke gas generated by the halogen flame retardant to human bodies and the environment during combustion is avoided. And finally, copolymerizing the small molecular flame retardant allyl phosphate diester and methacrylamide to prepare the macromolecular phosphorus-oxygen flame retardant, wherein the macromolecular flame retardant not only improves the synergistic effect of the allyl phosphate diester and the methacrylamide, but also avoids the migration and precipitation of the small molecular flame retardant in the high impact polystyrene resin matrix.
Therefore, the synergistic effect generated by the functional composite smoke suppressant and the macromolecular phosphorus-nitrogen flame retardant endows the HIPS resin with environmental protection, high efficiency and durability of flame retardant and smoke suppressant performances, solves the balance problem of the flame retardant performance and the mechanical performance of the HIPS resin, and prepares the flame retardant with the maximum smoke density of less than 80, the oxygen index of more than 42 percent and the cantilever beam notch impact strength of more than 10kJ/m 2 The environment-friendly low-smoke flame-retardant high impact polystyrene resin. The method has the characteristics of environmental protection, good smoke suppression efficiency, high flame retardant efficiency, low modification cost and the like.
Detailed Description
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The "parts" described in examples and comparative examples mean parts by mass.
Firstly, raw material sources:
high impact polystyrene (HIPS, 492J), MFR:2.9g/10min, china petrochemical Yanshan petrochemical Co
Solution polymerized styrene-butadiene rubber cement (SSBR 2564 s) with a solid content of 10%, of the oil-independent petrochemical company of China
Allyl diethyl phosphate, 98% purity, shanghai Mierel chemical technology Ltd
Methacrylamide, purity 99%, hubei Qifei pharmaceutical chemical Co., ltd
Aluminum hydroxide, particle size 2000 mesh, jinan Thaxing Fine chemical Co., ltd
Aluminum hypophosphite of 1000 mesh, shandong Jiu chemical Co., ltd
Glycol laurate, purity 99%, shanghai Jiachen chemical Co., ltd
Benzoyl Peroxide (BPO) half life T =133 ℃/1min, lanzhou adjuvant plant
Other reagents are all commercial products
Analysis and test method:
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 maximum smoke density: the assay was carried out as described in GB/T8323-1987.
Determination of notched Izod impact Strength: testing was carried out according to GB/T1843-1996.
Determination of graft ratio: taking about 4g of sample from a three-necked bottle by a pipette, weighing, adding 2-3 drops of hydroquinone solution, drying to constant weight, putting the sample in a Soxhlet fat extractor, extracting for 24h by toluene in a water bath at 90 ℃, and drying to constant weight. The monomer grafting was calculated as follows:
Figure 18773DEST_PATH_IMAGE002
in the formula: m is a unit of 0 -total mass of reactants (g); m-mass (g) of sample weighed after reaction; m is a unit of m -total mass of monomers in the reactants (g); m is SBR -mass (g) of solution polymerized styrene butadiene rubber in the sample; m is 1 -mass of sample after extraction (g).
Three equipment and instrument
Phi 34 twin-screw extruder Length/diameter =34/1 Lestreiz Germany
10L high-speed mixer Fuxin plastics machinery plant
15L coagulum (stirring type: two-layer three-blade inclined paddle) of Tianhua technology corporation, lanzhou
Example 1
(1) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g cyclohexane, 1000g SSBR2564s and 200g allyl diethyl phosphate into the polymerization kettle, heating to 60 ℃, adding 1.0g BPO, stirring for reaction for 6.0 hours, and then adding 10g diethylhydroxylamine as a terminator to prepare the graft solution-polymerized styrene-butadiene rubber cement (grafting rate: 5.1%).
b, preparing a functional composite smoke suppressant: adding 2000g of cyclohexane, 50g of glycol laurate and 10g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.0 by using sodium hydroxide, adding 600g of aluminum hydroxide and 400g of aluminum hypophosphite when the temperature is raised to 70 ℃, stirring and mixing for 2.0 hours, then adding 300g of graft solution-polymerized styrene-butadiene rubber cement (the grafting ratio is 5.1 percent), stirring and mixing for 4.0 hours, washing, drying and grinding to obtain the functional composite smoke suppressant.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of cyclohexane, 600g of allyl diethyl phosphate, 400g of methacrylamide and 1g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 0.5g of BPO when the temperature of the polymerization kettle reaches 50 ℃, reacting for 4.0hr, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant.
(3) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: putting 2000g of HIPS (492J), 200g of macromolecular phosphorus-nitrogen flame retardant, 100g of functional composite smoke suppressant, 5g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together, mixing at a 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 environment-friendly 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) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 1.
b, preparing a functional composite smoke suppressant: adding 2000g of cyclohexane, 60g of glycol laurate and 15g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.2 by using sodium hydroxide, adding 650g of aluminum hydroxide and 350g of aluminum hypophosphite when the temperature is raised to 70 ℃, stirring and mixing for 2.5 hours, then adding 320g of graft solution polymerized styrene-butadiene rubber cement (grafting ratio: 5.1%), stirring and mixing for 4.5 hours, washing, drying and grinding to obtain the functional composite smoke suppressant.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2200g of cyclohexane, 620g of allyl diethyl phosphate, 380g of methacrylamide and 2g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 1.0g of BPO when the temperature of the polymerization kettle reaches 55 ℃, reacting for 5.0hr, washing and drying to prepare the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin: 2000g of HIPS (492J), 250g of macromolecular phosphorus-nitrogen flame retardant, 120g of functional composite smoke suppressant, 6g of zinc stearate and 1010 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 6min, finally, the mixed materials are added into a phi 34 double-screw extruder, and 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 environment-friendly 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) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2500g of cyclohexane, 1000g of SSBR2564s and 240g of allyl diethyl phosphate into the polymerization kettle, heating to 70 ℃, adding 3.0g of BPO, stirring for reaction for 7.0 hours, and then adding 30g of diethylhydroxylamine as a terminator to prepare the graft solution-polymerized styrene-butadiene rubber cement (grafting rate: 7.3%).
b, preparing a functional composite smoke suppressant: adding 2500g of cyclohexane, 70g of glycol laurate and 20g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.5 by using sodium hydroxide, adding 700g of aluminum hydroxide and 300g of aluminum hypophosphite when the temperature is raised to 75 ℃, stirring and mixing for 3.0 hours, then adding 350g of graft solution polymerized styrene-butadiene rubber cement (the grafting ratio is 7.3 percent), stirring and mixing for 5.0 hours, washing, drying and grinding to obtain the functional composite smoke suppressant.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2500g of cyclohexane, 640g of allyl diethyl phosphate, 360g of methacrylamide and 3g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 1.5g of BPO when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.5 hours, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 300g of macromolecular phosphorus-nitrogen flame retardant, 140g of functional composite smoke suppressant, 8g of zinc stearate and 1010 5g of antioxidant into a 10L high-speed mixer, mixing at a high speed for 7min, and 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 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 environment-friendly 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) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
b, preparing a functional composite smoke suppressant: adding 2700g of cyclohexane, 80g of ethylene glycol laurate and 23g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.6 by using sodium hydroxide, adding 730g of aluminum hydroxide and 270g of aluminum hypophosphite when the temperature is raised to 75 ℃, stirring and mixing for 3.2 hours, then adding 370g of graft solution polymerized styrene-butadiene rubber cement (grafting ratio: 7.3%), stirring and mixing for 5.2 hours, washing, drying and grinding to obtain the functional composite smoke suppressant.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2600g of cyclohexane, 660g of allyl diethyl phosphate, 340g of methacrylamide and 4g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 2.0g of BPO when the temperature of the polymerization kettle reaches 63 ℃, reacting for 6.0hr, washing and drying to prepare the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin: 2000g of HIPS (492J), 340g of macromolecular phosphorus-nitrogen flame retardant, 160g of functionalized composite smoke suppressant, 9g of zinc stearate and 1010 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 8min, finally the mixed materials are added into a phi 34 twin-screw extruder, and 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 environment-friendly 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 a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
b, preparing a functional composite smoke suppressant: 2800g of cyclohexane, 90g of glycol laurate and 27g of KH-560 are added into a polymerization kettle, sodium hydroxide is used for regulating the pH value of the system to 9.8, 760g of aluminum hydroxide and 240g of aluminum hypophosphite are added when the temperature is raised to 75 ℃, the mixture is stirred and mixed for 3.6 hours, 380g of graft solution polymerized styrene-butadiene rubber cement (the grafting ratio is 7.3 percent) is added, the mixture is stirred and mixed for 5.5 hours, and the functionalized composite smoke suppressant is obtained by washing, drying and grinding.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 2800g of cyclohexane, 680g of allyl diethyl phosphate, 320g of methacrylamide and 4.5g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 2.5g of BPO when the temperature of the polymerization kettle reaches 67 ℃, reacting for 6.5 hours, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant.
(3) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: 2000g of HIPS (492J), 370g of macromolecular phosphorus-nitrogen flame retardant, 180g of functionalized composite smoke suppressant, 10g of zinc stearate and 1010 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 9min, finally the mixed materials are added into a phi 34 double-screw extruder, and 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 6min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of cyclohexane, 1000g of SSBR2564s and 300g of diethyl allylphosphate into the polymerization kettle, heating to 80 ℃, adding 5.0g of BPO, stirring for reaction for 8.0hr, and then adding 50g of diethylhydroxylamine as a terminator to prepare the graft solution-polymerized styrene-butadiene rubber cement (the grafting rate is 9.8%).
b, preparing a functional composite smoke suppressant: adding 3000g of cyclohexane, 100g of ethylene glycol laurate and 30g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 10.0 by using sodium hydroxide, adding 800g of aluminum hydroxide and 200g of aluminum hypophosphite when the temperature is raised to 80 ℃, stirring and mixing for 4.0h, then adding 400g of graft solution polymerized styrene-butadiene rubber cement (the grafting ratio is 9.8%), stirring and mixing for 6.0h, washing, drying and grinding to obtain the functional composite smoke suppressant.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of cyclohexane, 700g of allyl diethyl phosphate, 300g of methacrylamide and 5.0g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 3.0g of BPO when the temperature of the polymerization kettle reaches 70 ℃, reacting for 7.0hr, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin: 2000g of HIPS (492J), 400g of macromolecular phosphorus-nitrogen flame retardant, 200g of functionalized composite smoke suppressant, 12g of zinc stearate and 1010 8g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 10min, and finally the mixed materials are added 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, extrusion, cooling and granulation are carried out to obtain the environment-friendly 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 1
(1) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 1 except that the amount of diethyl allylphosphate added in the preparation of the graft solution polymerized styrene-butadiene latex was 150g, namely: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, adding 2000g of cyclohexane, 1000g of SSBR2564s and 150g of allyl diethyl phosphate into the polymerization kettle in sequence, heating to 60 ℃, adding 1.0g of BPO, stirring for reaction for 6.0hr, and then adding 10g of diethylhydroxylamine as a terminator to prepare the graft solution-polymerized styrene-butadiene rubber cement a (grafting rate: 3.9%).
b, preparing a functional composite smoke suppressant: the other conditions were the same as in example 1, except that the preparation of the functionalized composite smoke suppressant was carried out without adding the graft solution-polymerized styrene butadiene rubber cement (grafting ratio: 5.1%), but with adding the graft solution-polymerized styrene butadiene rubber cement a (grafting ratio: 3.9%) in an amount of 300g, that is: adding 2000g of cyclohexane, 50g of glycol laurate and 10g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.0 by using sodium hydroxide, adding 600g of aluminum hydroxide and 400g of aluminum hypophosphite when the temperature is raised to 70 ℃, stirring and mixing for 2.0 hours, then adding 300g of graft solution polymerized styrene-butadiene rubber cement a (grafting ratio: 3.9%), stirring and mixing for 4.0 hours, washing, drying and grinding to obtain the functional composite smoke suppressant a.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the same as in example 1.
(3) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: the difference lies in that the functionalized composite smoke suppressant is not added in the preparation process of the environment-friendly low-smoke flame-retardant high-impact polystyrene resin, but the functionalized composite smoke suppressant a is added, the addition amount is 100g, namely: 2000g of HIPS (492J), 200g of macromolecular phosphorus-nitrogen flame retardant, 100g of functionalized composite smoke suppressant a, 5g of zinc stearate and 1010 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 5min, and finally the mixed materials are added 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 environment-friendly 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 "phosphorus-nitrogen" flame retardant: the same as in example 2.
(2) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: the difference lies in that the functionalized composite smoke suppressant is not added in the preparation process of the environment-friendly low-smoke, flame-retardant and high impact polystyrene resin, but aluminum hydroxide is directly added, the addition amount is 120g, namely: 2000g of HIPS (492J), 250g of macromolecular phosphorus-nitrogen flame retardant, 120g of aluminum hydroxide, 6g of zinc stearate and 1010 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 6min, finally, the mixed materials are added into a phi 34 twin-screw extruder, and 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, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparing a functional composite smoke suppressant: the other conditions are the same as the example 3, except that the preparation process of the functionalized composite smoke suppressant is not added with the graft solution polymerized styrene-butadiene rubber cement (grafting ratio: 7.1 percent), namely: adding 2500g of cyclohexane, 70g of ethylene glycol laurate and 20g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.5 by using sodium hydroxide, adding 700g of aluminum hydroxide and 300g of aluminum hypophosphite when the temperature is raised to 75 ℃, stirring and mixing for 3.0h, washing, drying and grinding to obtain the functionalized composite smoke suppressant b.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the same as in example 3.
(3) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: the difference lies in that no functionalized composite smoke suppressant is added in the preparation process of the environment-friendly low-smoke, flame-retardant and high impact polystyrene resin, but a functionalized composite smoke suppressant b is added, the addition amount is 140g, namely: 2000g of HIPS (492J), 300g of macromolecular phosphorus-nitrogen flame retardant, 140g of functionalized composite smoke suppressant b, 8g of zinc stearate and 1010 5g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 7min, and finally the mixed materials are added 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 environment-friendly 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) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 4.
b, preparing a functional composite smoke suppressant: the other conditions were the same as in example 4, except that no aluminum hypophosphite was added during the preparation of the functionalized composite smoke suppressant, i.e.: adding 2700g of cyclohexane, 80g of ethylene glycol laurate and 23g of KH-560 into a polymerization kettle, adjusting the pH value of the system to 9.6 by using sodium hydroxide, adding 730g of aluminum hydroxide when the temperature is raised to 75 ℃, stirring and mixing for 3.2 hours, then adding 370g of graft solution polymerized styrene-butadiene rubber cement (the grafting ratio is 7.3 percent), stirring and mixing for 5.2 hours, washing, drying and grinding to obtain the functionalized composite smoke suppressant c.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the same as in example 4.
(3) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: the difference lies in that no functionalized composite smoke suppressant is added in the preparation process of the environment-friendly low-smoke, flame-retardant and high impact polystyrene resin, but a functionalized composite smoke suppressant c is added, the addition amount is 160g, namely: 2000g of HIPS (492J), 340g of macromolecular phosphorus-nitrogen flame retardant, 160g of functionalized composite smoke suppressant c, 9g of zinc stearate and 1010 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 8min, and finally the mixed materials are added 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 environment-friendly 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 5
(1) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 5.
b, preparing a functional composite smoke suppressant: the same as in example 5.
(2) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: the difference lies in that in the preparation process of the environment-friendly low-smoke flame-retardant high impact polystyrene resin, a macromolecular phosphorus-nitrogen flame retardant is not added, and instead, a micromolecular flame retardant methacrylamide is added, wherein the addition amount is 370g, namely: putting 2000g of HIPS (492J), 370g of methacrylamide, 180g of functionalized composite smoke suppressant, 10g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together, mixing at high speed for 9min, and 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 in sequence: 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 environment-friendly 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) Preparing a functional composite smoke suppressant:
a, preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 6.
b, preparing a functional composite smoke suppressant: the same as in example 6.
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the same as in example 6.
(3) The preparation of the environment-friendly low-smoke flame-retardant high impact polystyrene resin comprises the following steps: the difference lies in that the addition amount of the functionalized composite smoke suppressant in the preparation process of the environment-friendly low-smoke flame-retardant high impact polystyrene resin is 70g, namely: 2000g of HIPS (492J), 400g of macromolecular phosphorus-nitrogen flame retardant, 70g of functionalized composite smoke suppressant, 12g of zinc stearate and 1010 8g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 10min, and finally the mixed materials are added 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 6min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of Environment-friendly Low-Smoke, high-flame-retardant, high-impact polystyrene resin
Sample numbering Oxygen index% Maximum smoke density Combustion characteristic Impact strength kJ/m2 of cantilever beam notch
Example 1 42.3 79 Class V-0 10.1
Example 2 42.7 72 Class V-0 10.6
Example 3 43.1 68 Class V-0 11.4
Example 4 43.5 65 Class V-0 11.6
Example 5 43.9 60 Class V-0 12.1
Example 6 44.3 55 Class V-0 11.8
Comparative example 1 30.2 126 Can not grade 8.9
Comparative example 2 21.3 239 Can not grade 3.8
Comparative example 3 30.6 141 Can not grade 2.9
Comparative example 4 35.9 115 Class V-2 7.3
Comparative example 5 26.3 112 Can not grade 7.8
Comparative example 6 37.7 103 Class V-2 9.7
Reference sample 18.9 276 Cannot grade 6.3
Reference sample * : the polystyrene (492J) is commercially available from Yanshan petrochemical company, china petrochemical company.

Claims (12)

1. An environment-friendly low-smoke flame-retardant high-impact polystyrene resin composition comprises the following components in parts by mass: 100 parts of high impact polystyrene resin; (2) 10 to 20 parts of macromolecular phosphorus-nitrogen flame retardant; (3) 5 to 10 parts of a functional composite smoke suppressant; (4) 0.2 to 0.6 part of a stabilizer; (5) 0.1 to 0.5 part of antioxidant, which is characterized in that:
the functionalized composite smoke suppressant is a core-shell structure substance which takes a composite of two smoke suppressants, namely aluminum hydroxide and aluminum hypophosphite, as a core and takes solution polymerized styrene-butadiene rubber cement as a shell;
the structural general formula of the macromolecular phosphorus-nitrogen flame retardant is as follows:
Figure 429409DEST_PATH_IMAGE001
in the formula: r is C 1 ～C 8 M and n are the number of repeating units;
the preparation method of the environment-friendly low-smoke flame-retardant high-impact polystyrene resin composition comprises the following steps:
(1) Preparing a functional composite smoke suppressant:
a. preparing graft solution polymerized styrene-butadiene rubber cement: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 to 4 times, sequentially adding 200 to 300 parts of solvent, 100 parts of solution-polymerized styrene-butadiene rubber cement and 20 to 30 parts of allyl phosphate diester into the reaction kettle, adding 0.1 to 0.5 part of initiator when the temperature is raised to 60 to 80 ℃, stirring for reaction for 6.0 to 8.0 hours, and then adding 1.0 to 5.0 parts of terminator to prepare graft solution-polymerized styrene-butadiene rubber cement, wherein the grafting ratio is 5.0 to 10.0%;
b. preparing a functional composite smoke suppressant: adding 200 to 300 parts of solvent, 5 to 10 parts of polyol laurate and 1.0 to 3.0 parts of silane coupling agent into a reaction kettle according to 100 parts of total mass of the smoke suppressant, adjusting the pH value of the system to be 9.0 to 10.0 by using a buffer, adding 60 to 80 parts of aluminum hydroxide and 20 to 40 parts of aluminum hypophosphite when the temperature is raised to 70 to 80 ℃, stirring and mixing for 2.0 to 4.0 hours, then adding 30 to 40 parts of graft solution-polymerized styrene-butadiene rubber slurry, stirring and mixing for 4.0 to 6.0 hours, washing, drying and grinding to obtain the functional composite smoke suppressant;
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: taking the total mass of the reactive flame retardant as 100 parts, firstly introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 to 4 times, sequentially adding 200 to 300 parts of solvent, 60 to 70 parts of allyl phosphate diester, 30 to 40 parts of methacrylamide and 0.1 to 0.5 part of molecular weight regulator into the reaction kettle, stirring, mixing and heating, adding 0.05 to 0.3 part of initiator when the temperature of the reaction kettle reaches 50 to 70 ℃, reacting for 4.0 to 7.0 hours, washing and drying after the reaction is finished, and preparing a macromolecular phosphorus-nitrogen flame retardant;
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin composition: adding 100 parts of high impact polystyrene resin, 10 to 20 parts of macromolecular phosphorus-nitrogen flame retardant, 5 to 10 parts of functionalized composite smoke suppressant, 0.2 to 0.6 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 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 environment-friendly low-smoke flame-retardant high-impact polystyrene resin composition.
2. The environmentally friendly, low smoke, flame retardant, high impact polystyrene resin composition of claim 1, wherein said diallyl phosphate is one of dimethyl allyl phosphate, diethyl allyl phosphate, dipropyl allyl phosphate, dibutyl allyl phosphate, dipentyl allyl phosphate, dihexyl allyl phosphate, diheptyl allyl phosphate, and dioctyl allyl phosphate.
3. The environment-friendly low-smoke, flame-retardant high-impact polystyrene resin composition of claim 2, wherein said allyl diphosphate is diethyl allyl phosphate.
4. The environment-friendly low-smoke, flame-retardant high-impact polystyrene resin composition as claimed in claim 1, wherein said molecular weight modifier is one selected from the group consisting of tertiary decamercaptan, tertiary dodecanethiol, tertiary tetradecanethiol and tertiary hexadecanethiol.
5. The environmentally friendly, low smoke, flame retardant high impact polystyrene resin composition of claim 4, wherein said molecular weight modifier is tertiary dodecyl mercaptan.
6. The environment-friendly low-smoke, flame-retardant high-impact polystyrene resin composition of claim 1, wherein said initiator is one selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide and di-t-butyl peroxide.
7. The environmentally friendly, low smoke, flame retardant, high impact polystyrene resin composition of claim 6, wherein said initiator is benzoyl peroxide.
8. The environment-friendly low-smoke flame-retardant high-impact polystyrene resin composition as claimed in claim 1, wherein the solid content of the solution-polymerized styrene-butadiene rubber cement is 5-20 w%.
9. The environment-friendly low-smoke, flame-retardant high-impact polystyrene resin composition as claimed in claim 1, wherein said polyol laurate is selected from one or more of ethylene glycol laurate, propylene glycol laurate, glycerol laurate, butylene glycol laurate, and pentaerythritol laurate.
10. The environment-friendly low-smoke, flame-retardant high-impact polystyrene resin composition as claimed in claim 1, wherein the silane coupling agent is one selected from 3-glycidoxypropyltrimethoxysilane, N- β -aminoethyl- γ -aminopropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, and vinyltrimethoxysilane.
11. The environmentally friendly low smoke, flame retardant high impact polystyrene resin composition of claim 10, wherein said silane coupling agent is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane.
12. A method for preparing the environment-friendly low-smoke flame-retardant high impact polystyrene resin composition as claimed in claim 1, which is characterized in that the preparation process comprises the following steps:
(1) Preparing a functional composite smoke suppressant:
a. preparing graft solution polymerized styrene-butadiene rubber cement: taking the mass of the solution-polymerized styrene-butadiene rubber cement as 100 parts, firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 to 4 times, sequentially adding 200 to 300 parts of solvent, 100 parts of solution-polymerized styrene-butadiene rubber cement and 20 to 30 parts of allyl phosphate diester into the reaction kettle, adding 0.1 to 0.5 part of initiator when the temperature is raised to 60 to 80 ℃, stirring for reaction for 6.0 to 8.0 hours, and then adding 1.0 to 5.0 parts of terminator to prepare graft solution-polymerized styrene-butadiene rubber cement, wherein the grafting ratio is 5.0 to 10.0%;
b. preparing a functional composite smoke suppressant: adding 200 to 300 parts of solvent, 5 to 10 parts of polyol laurate and 1.0 to 3.0 parts of silane coupling agent into a reaction kettle according to 100 parts of the total mass of the smoke suppressant, adjusting the pH value of the system to be 9.0 to 10.0 by using a buffering agent, adding 60 to 80 parts of aluminum hydroxide and 20 to 40 parts of aluminum hypophosphite when the temperature is raised to 70 to 80 ℃, stirring and mixing for 2.0 to 4.0 hours, then adding 30 to 40 parts of graft solution-polymerized styrene-butadiene rubber cement, stirring and mixing for 4.0 to 6.0 hours, washing, drying and grinding to obtain the functional composite smoke suppressant;
(2) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: taking the total mass of the reactive flame retardant as 100 parts, firstly introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 to 4 times, sequentially adding 200 to 300 parts of solvent, 60 to 70 parts of allyl phosphate diester, 30 to 40 parts of methacrylamide and 0.1 to 0.5 part of molecular weight regulator into the reaction kettle, stirring, mixing and heating, adding 0.05 to 0.3 part of initiator when the temperature of the reaction kettle reaches 50 to 70 ℃, reacting for 4.0 to 7.0 hours, washing and drying after the reaction is finished, and preparing the macromolecular phosphorus-nitrogen flame retardant;
(3) Preparation of environment-friendly low-smoke flame-retardant high impact polystyrene resin composition: taking 100 parts of high impact polystyrene resin as a base material, adding 100 parts of the high impact polystyrene resin, 10 to 20 parts of macromolecular phosphorus-nitrogen flame retardant, 5 to 10 parts of functionalized composite smoke suppressant, 0.2 to 0.6 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; 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 environment-friendly low-smoke flame-retardant high impact polystyrene resin composition.
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