1. A high flame-retardant, low-smoke and high-impact polystyrene resin composition comprises the following components in parts by mass: (1) 100 parts of high impact polystyrene resin; (2) 10-20 parts of macromolecular phosphorus-halogen flame retardant; (3) 1-5 parts of grafted high impact polystyrene; (4) 5-10 parts of a functional smoke suppressant; (5) 0.2-0.6 part of a stabilizer; (6) 0.1-0.3 part of antioxidant, which is characterized in that:

the functional smoke suppressant is a core-shell structural substance taking the smoke suppressant as a core and the carboxylated styrene butadiene rubber as a shell;

the molecular chain of the grafted high impact polystyrene contains carboxyl;

the structural general formula of the macromolecular phosphorus-halogen flame retardant is as follows:

in the formula: x is a halogen element, R is C₁～C₈M and n are the number of repeating units.

2. The highly flame retardant, low smoke, high impact polystyrene resin composition of 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 to 20g/10 min.

3. The highly flame retardant, low smoke, high impact polystyrene resin composition of claim 1 wherein said smoke suppressant is selected from the group consisting of montmorillonite, kaolin, hydrotalcite, calcium carbonate, kaolin and barium sulfate.

4. A high flame retardant, low smoke, high impact polystyrene resin composition as claimed in claim 3 wherein said smoke suppressant is kaolin.

5. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 1, characterized in that the process comprises: the method comprises the following steps of introducing inert gas into a reaction kettle for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 70-80 parts of allyl phosphate diester, 20-30 parts of allyl acyl halide and 0.1-0.5 part of molecular weight regulator into the reaction kettle, stirring, mixing and heating, adding 0.05-0.3 part of initiator when the temperature of the reaction kettle reaches 50-70 ℃, reacting for 4.0-7.0 hr, washing and drying after the reaction is finished, and obtaining the macromolecular phosphorus-halogen flame retardant.

6. A method of preparing a macromolecular phosphorus-halogen flame retardant according to claim 5, 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.

7. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 6, characterized in that said diallyl phosphate is diethyl allylphosphate.

8. The method of claim 5, wherein the allyl acyl halide is one of allyl acyl bromide and allyl acyl chloride.

9. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 8, characterized in that the allylic halide is allylic bromide.

10. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 3, characterized in that the molecular weight regulator is selected from one of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan.

11. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 12, characterized in that said molecular weight regulator is tert-dodecyl mercaptan.

12. A process for preparing the grafted high impact polystyrene as claimed in claim 1, characterized in that it is prepared by: mixing 0.5-1.0% of initiator and solvent for 5-10 min by taking the high impact polystyrene resin as 100 parts, wherein the weight ratio of the solvent to the initiator is 3: 1-5: 1; then adding the high impact polystyrene resin, 5-10% of polar monomer and the mixed initiator into a high-speed mixer, and mixing for 10-15 min at high speed; and adding the mixed materials into a screw kneading machine, reacting at the temperature of 170-200 ℃ for 6-12 min, extruding, cooling and granulating to obtain the initiated high impact polystyrene.

13. A process according to either of claims 5 and 12, wherein the initiator is an organic peroxide selected from the group consisting of 1, 1-dimethylethyl-hydroperoxide, t-butyl hydroperoxide, di-t-butyl hydroperoxide and teramyl hydroperoxide.

14. The method of claim 13 wherein said initiator is t-butyl hydroperoxide.

15. A method for preparing the functionalized smoke suppressant of claim 1, characterized by the steps of: adding 300-400 parts of deionized water, 5.0-10.0 parts of emulsifier and 40-50 parts of carboxylic styrene-butadiene latex into a polymerization kettle by taking the mass of the smoke suppressant as 100 parts, heating to 50-60 ℃, adding 100 parts of smoke suppressant and 1.0-5.0 parts of titanate coupling agent, stirring and mixing for 50-70 min, adjusting the pH value of the system to 9.0-10.0 by using a buffering agent, then adding 2.0-5.0 parts of separant and 3.0-6.0 parts of coagulant, heating to 80-90 ℃, stirring for 10-20 min for curing, dehydrating, drying and grinding to obtain the functional smoke suppressant.

16. The method of claim 15 wherein the titanate coupling agent is selected from the group consisting of isopropyl dioleate acyloxy titanate, dioctyl phosphate acyloxy titanate, isopropyl trioleate acyloxy titanate, dodecylbenzene sulfonyl titanate, dioctyl pyrophosphate acyloxy titanate, and dioctyl phosphite acyloxy titanate.

17. A method for preparing the highly flame-retardant, low-smoke, high-impact polystyrene resin composition as defined in claim 1, which is characterized by comprising the steps of: according to 100 parts by mass of the high impact polystyrene resin, 100 parts of the high impact polystyrene resin, 10-20 parts of macromolecular phosphorus-halogen flame retardant, 1-5 parts of grafted high impact polystyrene, 5-10 parts of functionalized smoke suppressant, 0.2-0.6 part of stabilizer and 0.1-0.3 part of antioxidant are uniformly mixed, and then the mixture is directly added into a screw kneading machine, the reaction temperature is 160-200 ℃, the reaction time is 4-6 min, and the mixture is extruded, cooled and granulated to obtain the high flame-retardant, low-smoke and high impact polystyrene resin.

18. The method for preparing a highly flame retardant, low smoke, high impact polystyrene resin composition as claimed in claim 17, wherein said screw kneader is selected from the group consisting of a single screw extruder and a multi-screw extruder.

19. The method for preparing a highly flame retardant, low smoke, high impact polystyrene resin composition as claimed in claim 18, wherein said screw kneader is a twin screw extruder.

Background

High Impact Polystyrene (HIPS) has the advantages of excellent formability, good toughness, high dimensional stability, 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, the halogen-containing micromolecule flame retardant is generally adopted to prepare the flame-retardant resin, and the flame-retardant resin has the advantages of high flame retardance, generation of a large amount of smoke and toxic substances during combustion, difficulty in breathing of people, more serious harm than result generated by combustion, and the possibility of being the first risk factor of casualties in fire. In recent years, people have higher and higher requirements on fire safety and flame retardance and low smoke performance of products, and research on developing novel high-flame retardance and low-smoke 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 with surface treated by sulfonated high impact polystyrene, which is mixed with high impact polystyrene resin to prepare a flame retardant with impact strength of 5.4kJ/m²And 29% oxygen index. CN101353461A discloses a flame-retardant high impact polystyrene compound 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. Right quartz, etc. with organic flame retardantsThe impact strength of the notch of the simply supported beam prepared by compounding tetrabromobisphenol A, inorganic flame retardant hydrated magnesium oxide and antimony trioxide can reach 25.3kJ/m²And the flame retardant property of the low-smoke flame-retardant HIPS resin reaches UL 94V-0 level (Chinese plastics, 2003,17(8): 39-42).

These patents and documents describe modification with small molecular halogen-based organic flame retardants and inorganic powder flame retardants, and although significant effects have been achieved in improving the flame retardancy of HIPS resins, problems such as large amount of flame retardants used, high modification cost, and large adverse effects on the impact strength properties of the materials have arisen.

Disclosure of Invention

The invention aims to provide a high-performance high-smoke-density high-oxygen-index high-oxygen-content high-molecular-weight carbon material with the maximum smoke density of less than 130, the oxygen index of more than 41 percent and the notched impact strength of a cantilever beam of more than 7kJ/m²The preparation method of the high flame-retardant, low-fuming and high-impact polystyrene resin. Firstly, adopting allyl phosphate diester and allyl acyl halide to carry out copolymerization to generate a macromolecular phosphorus-halogen flame retardant, and then grafting HIPS resin by using organic carboxylic acid to prepare grafted HIPS; secondly, coating the inorganic smoke suppressant with carboxylic styrene butadiene latex; and finally, directly blending and granulating the macromolecular phosphorus-halogen flame retardant, the grafted HIPS, the functionalized smoke suppressant and the high impact polystyrene resin to prepare the high flame retardant, low smoke and high impact polystyrene resin. The method gives full play to the high-efficiency flame retardance and the stability of the macromolecular flame retardant, takes the grafted HIPS as a compatible system to obviously improve the compatibility of the macromolecular flame retardant and the smoke suppressant with the high-impact polystyrene resin, solves the problems of uneven dispersion, migration, precipitation and the like of the flame retardant and the smoke suppressant in a resin matrix, gives full play to the high-efficiency flame retardance of the macromolecular flame retardant on the premise of ensuring the mechanical property, and endows the HIPS resin with low smoke generation.

The "parts" in the present invention mean parts by mass.

The preparation of the high-flame-retardant, low-smoke and 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: adding 300-400 parts of deionized water, 5.0-10.0 parts of emulsifier and 40-50 parts of carboxylic styrene-butadiene latex into a polymerization kettle by taking the mass of the smoke suppressant as 100 parts, heating to 50-60 ℃, adding 100 parts of smoke suppressant and 1.0-5.0 parts of titanate coupling agent, stirring and mixing for 50-70 min, adjusting the pH value of the system to 9.0-10.0 by using a buffering agent, then adding 2.0-5.0 parts of separant and 3.0-6.0 parts of coagulant, heating to 80-90 ℃, stirring for 10-20 min for curing, dehydrating, drying and grinding to obtain the functional smoke suppressant.

(2) Preparation of macromolecular "phosphorus-halogen" flame retardant: based on 100 parts of the total mass of the reaction flame retardant, firstly introducing inert gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 70-80 parts of allyl phosphate diester, 20-30 parts of allyl acyl halide and 0.1-0.5 part of molecular weight regulator into a polymerization kettle, stirring, mixing and heating, adding 0.05-0.3 part of initiator when the temperature of the polymerization kettle reaches 50-70 ℃, reacting for 4.0-7.0 hr, washing and drying after the reaction is finished, and preparing the macromolecular phosphorus-halogen flame retardant.

(3) Preparation of grafted HIPS: mixing 0.5-1.0% of initiator and solvent for 5-10 min by taking the high impact polystyrene resin as 100 parts, wherein the weight ratio of the solvent to the initiator is 3: 1-5: 1; then adding the HIPS resin, 5-10% of polar monomer and the mixed initiator into a high-speed mixer and mixing for 10-15 min at high speed; and adding the mixed materials into a double-screw extruder, reacting at the temperature of 170-200 ℃ for 6-12 min, extruding, cooling and granulating to obtain the grafted HIPS (the grafting rate is 2.0-5.0%).

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: adding 100 parts of high impact polystyrene resin, 10-20 parts of macromolecular phosphorus-halogen flame retardant, 1-5 parts of grafted HIPS, 5-10 parts of functionalized smoke suppressant, 0.2-0.6 part of stabilizer and 0.1-0.3 part of antioxidant into a high-speed mixer, and mixing for 5-10 min, 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 high-flame-retardant, low-smoke and high-impact polystyrene resin.

The macromolecular phosphorus-halogen flame retardant has the following structural general formula:

in the formula: x is halogen element bromine and chlorine; r is C₁～C₈Alkyl group of (1). The allyl acyl halide is one of allyl acyl bromide and allyl acyl chloride, and preferably allyl acyl bromide. 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 powdery or granular resin, and has a Melt Flow Rate (MFR) of 0.5-20 g/10 min.

The smoke inhibitor is selected from one of montmorillonite, kaolin, hydrotalcite, calcium carbonate and barium sulfate, and the kaolin is preferred.

The carboxylic styrene-butadiene latex is obtained by taking butadiene and styrene as main monomers and unsaturated carboxylic acid as a functional monomer through emulsion polymerization, wherein the unsaturated carboxylic acid is acrylic acid, methacrylic acid or 2-ethyl acrylic acid, and acrylic acid is preferred. The solid content of the carboxylic styrene-butadiene latex is 40-55%, and the combined acid is 5-15%.

The initiator is an organic peroxide, and is selected from one of 1, 1-dimethylethyl-hydroperoxide (TB), tert-butyl hydroperoxide (TBHP), di-tert-butyl hydroperoxide and tert-amyl hydroperoxide (TAHP) TBHP, and preferably tert-butyl hydroperoxide (TBHP).

The polar monomer is selected from one of Maleic Anhydride (MAH), Acrylic Acid (AA), methacrylic acid (MAA) and ethacrylic acid, and acrylic acid (MAA) is preferred. TBHP

The molecular weight regulator of the present invention may be selected from one of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan, and tertiary dodecyl mercaptan is preferred.

The titanate coupling agent is selected from one of isopropyl dioleate acyloxy titanate (NDZ-101), dioctyl phosphate acyloxy titanate (NDZ-102), isopropyl trioleate acyloxy titanate (NDZ-105), dodecylbenzene sulfonyl titanate (NDZ-109), dioctyl pyrophosphate acyloxy titanate (NDZ-201) and dioctyl phosphite acyloxy titanate (NDZ-401), and is preferably NDZ-101.

The screw kneader according to the invention can be a single-screw extruder or a multi-screw extruder, preferably a twin-screw extruder.

The inert gas according to the present invention may be one of rare gases of group 0 other than radon, preferably argon.

The solvent, antioxidant, stabilizer, emulsifier, release agent, coagulant, buffer and the like 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, cyclopentane, 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 emulsifier is selected from one of carboxylate, fatty acid soap, abietic acid soap, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and polyoxyethylene sorbitan monooleate, and the sodium dodecyl benzene sulfonate is preferred.

The separant can be one selected from potassium stearate, sodium stearate, potassium oleate, sodium oleate, synthetic fatty acid potassium and synthetic fatty acid sodium.

The coagulant of the present invention may be one or more selected from monovalent metal salt, divalent metal salt, and divalent metal salt. For example: one of sodium chloride, magnesium chloride, ferric chloride, calcium chloride, magnesium sulfate, aluminum sulfate and alum.

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 invention firstly coats the surface of the smoke inhibitor, and adds the carboxylic styrene-butadiene latex to form a 'core-shell' structure which takes the smoke inhibitor as a core and the carboxylic styrene-butadiene rubber as a shell, and the 'shell' contains a styrene chain segment, a butadiene chain segment with a1, 4 structure and a carboxyl group, thereby playing two roles: on one hand, the shell has a styrene chain segment, the chain segment contains a benzene ring structure, and the shell has the characteristics of non-polarity and large steric hindrance, thereby effectively preventing the agglomeration of the powdery smoke suppressant particles and improving the smoke suppressant effect. On the other hand, the modified smoke suppressant has a toughening effect, and the modified smoke suppressant contains a certain amount of polybutadiene chain segments with 1,4 structures, so that the reduction of the impact resistance of the HIPS resin caused by the introduction of a rigid inorganic smoke suppressant is avoided.

Secondly, the invention adopts micromolecule flame retardant allyl phosphodiester and allyl halide to carry out copolymerization to prepare the macromolecular flame retardant of macromolecular 'phosphorus-halide', the flame retardant not only avoids the migration and the precipitation of the micromolecule flame retardant in the high impact polystyrene resin matrix, but also improves the durability of the flame retardant effect. Finally, the HIPS is grafted, the grafted HIPS plays the role of a coupling agent, the carboxyl in the grafted HIPS can generate adsorption with polar group ester groups, acyl groups and halogen atoms in the macromolecular phosphorus-halogen flame retardant and also generate adsorption with carboxyl in the functionalized smoke suppressant shell, can obviously improve the compatibility of the macromolecular phosphorus-halogen composite flame retardant and the functionalized smoke suppressant with the high impact polystyrene resin, solves the problem that the macromolecular phosphorus-halogen composite flame retardant and the functionalized smoke suppressant are not uniformly dispersed in the high impact polystyrene resin matrix, the synergistic effect of the macromolecular 'phosphorus-halogen' flame retardant and the functional smoke suppressant on the flame retardance is obviously improved, the flame retardance and the smoke suppression effect are obviously enhanced, therefore, the dosage of the halogen-containing flame retardant is reduced on the premise of ensuring the flame retardant effect, and a large amount of halogen-containing flame retardant generated by combustion is avoided.The toxic smoke has harm to human body and environment. Therefore, the synergistic and coupling effect generated by the macromolecular 'phosphorus-halogen' flame retardant, the grafted HIPS and the functionalized smoke suppressant solves the balance problem of the flame retardant property and the mechanical property of the HIPS resin, endows the HIPS resin with high efficiency and durability of the flame retardant property and the smoke suppressant property, and prepares the flame retardant with the maximum smoke density of less than 130, the oxygen index of more than 41 percent and the notched impact strength of a cantilever beam of more than 7kJ/m²The high flame-retardant, low-fuming and high-impact polystyrene resin. The method has the characteristics of low addition proportion, high smoke abatement efficiency, good flame retardant effect, low modification cost and the like.

Firstly, raw material sources:

high impact polystyrene (HIPS, 492J), MFR: 2.9g/10min, China petrochemical Yanshan petrochemical Co

Allyl diethyl phosphate purity 98%, Shanghai Mirui chemical technology Co., Ltd

Allyl bromide, purity 99%, Hangzhou Weikang scientific and technological Limited

Allyl chloride, purity 99%, Hangzhou Weikang scientific and technological Co., Ltd

Kaolin Fine chemical Co., Ltd of 900 mesh size

The carboxylic styrene-butadiene latex combined acid is 7 percent, and the research institute of petroleum and chemical industry

Isopropyldioleacyloyloxytitanate (NDZ-101) Huaian Kazai Co Ltd

Tert-butyl hydroperoxide (TBHP) Lanzhou auxiliary factory

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.

Determination of the graft ratio: taking about 4g of sample from a three-necked bottle by using a pipette, weighing, adding 2-3 drops of hydroquinone solution, drying to constant weight, putting the sample in a Soxhlet fat extractor, extracting and extracting for 24 hours by using toluene in a water bath at 90 ℃, and drying to constant weight. The monomer grafting was calculated as follows:

in the formula: m is₀-total mass of reactants (g); m-sample mass (g) weighed after reaction; m is_m-total mass of monomers in the reactants (g); m is_SBR-mass (g) of high impact polystyrene resin in the sample; m is₁-mass of sample after extraction (g).

Device and instrument for performing the following steps

Phi 34 twin screw extruder length/diameter 34/1 Lestreiz Germany

10L high-speed mixer Fuxin plastics machinery plant

15L coagulum kettle (stirring type: two-layer three-blade inclined paddle) of Tian Hua Koch Tech Co., Lanzhou

Example 1

(1) Preparing a functional smoke suppressant: adding 3000g of deionized water, 50g of sodium dodecyl benzene sulfonate and 400g of carboxylic styrene-butadiene latex into a 15L stainless steel polymerization kettle, adding 1000g of kaolin and NDZ-10110 g when the temperature is raised to 50 ℃, stirring and mixing for 50min, adjusting the pH value of the system to 9.0 by using sodium hydroxide, then adding 20g of sodium oleate and 30g of magnesium sulfate, heating to 80 ℃, stirring for 10min for curing, and then dehydrating, drying and grinding to obtain the functionalized kaolin.

(2) Preparation of macromolecular "phosphorus-halogen" 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, 800g of allyl diethyl phosphate, 200g of allyl bromide and 1g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 0.5g of TBHP when the temperature of the polymerization kettle reaches 50 ℃, reacting for 4.0hr, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.

(3) Preparation of grafted HIPS: 15g of toluene and 5g of TBHP are put into a beaker and mixed for 5min, the mixed liquid, 1000g of HIPS (492J) and 50g of Acrylic Acid (AA) are put into a 10L high-speed mixer and mixed for 10min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 6min, the HIPS-g-AA graft (grafting rate 2.1%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 200g of macromolecular phosphorus-bromine flame retardant, HIPS-g-AA20g, 100g of functionalized kaolin, 5g of stearic acid and 10103 g of antioxidant into a 10L high-speed mixer to mix 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 high-flame-retardant, low-smoke and 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 smoke suppressant: 3200g of deionized water, 60g of sodium dodecyl benzene sulfonate and 420g of carboxylic styrene-butadiene latex are added into a 15L stainless steel polymerization kettle, 1000g of kaolin and NDZ-10120 g are added when the temperature is raised to 52 ℃, after stirring and mixing for 55min, the pH value of the system is adjusted to 9.2 by using sodium hydroxide, 25g of sodium oleate and 35g of magnesium sulfate are added, the mixture is stirred for 12min when the temperature is raised to 82 ℃ for curing, and then the functionalized kaolin is obtained through dehydration, drying and grinding.

(2) Preparation of macromolecular "phosphorus-halogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2300g of cyclohexane, 780g of allyl diethyl phosphate, 220g of allyl bromide and 1.5g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 0.9g of TBHP when the temperature of the polymerization kettle reaches 55 ℃, reacting for 4.5 hours, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.

(3) Preparation of grafted HIPS: 20g of toluene and 6g of TBHP are put into a beaker and mixed for 6min, the mixed liquid, 1000g of HIPS (492J) and 60g of Acrylic Acid (AA) are put into a 10L high-speed mixer and mixed for 11min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 7min, the HIPS-g-AA graft (grafting rate 2.7%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 250g of macromolecular phosphorus-bromine flame retardant, HIPS-g-AA40g, 130g of functionalized kaolin, 6g of zinc stearate and 10104 g of antioxidant into a 10L high-speed mixer to mix at high speed for 6 min; 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 4.5min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: 3500g of deionized water, 70g of sodium dodecyl benzene sulfonate and 440g of carboxylic styrene-butadiene latex are added into a 15L stainless steel polymerization kettle, 1000g of kaolin and NDZ-10130 g are added when the temperature is raised to 55 ℃, after stirring and mixing for 60min, the pH value of the system is adjusted to 9.5 by using sodium hydroxide, 30g of sodium oleate and 40g of magnesium sulfate are added, the temperature is raised to 85 ℃, stirring for 15min is carried out for curing, and then dehydration, drying and grinding are carried out to obtain the functionalized kaolin.

(2) Preparation of macromolecular "phosphorus-halogen" 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, 760g of allyl diethyl phosphate, 240g of allyl bromide and 2.0g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 1.5g of TBHP when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.0hr, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.

(3) Preparation of grafted HIPS: 26g of toluene and 7g of TBHP are put into a beaker and mixed for 7min, the mixed liquid, 1000g of HIPS (492J) and 70g of Acrylic Acid (AA) are put into a 10L high-speed mixer together and mixed for 12min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 9min, the HIPS-g-AA graft (grafting rate 3.4%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 290g of macromolecular phosphorus-bromine flame retardant, HIPS-g-AA50g, 150g of functionalized kaolin, 8g of zinc stearate and 10105g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 7 min; 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 5.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: 3700g of deionized water, 80g of sodium dodecyl benzene sulfonate and 460g of carboxylic styrene-butadiene latex are added into a 15L stainless steel polymerization kettle, 1000g of kaolin and NDZ-10140g are added when the temperature is raised to 56 ℃, after stirring and mixing for 63min, the pH value of the system is adjusted to 9.7 by sodium hydroxide, then 40g of sodium oleate and 45g of magnesium sulfate are added, the system is stirred for 16min when the temperature is raised to 87 ℃ for curing, and then the functionalized kaolin is obtained through dehydration, drying and grinding.

(2) Preparation of macromolecular "phosphorus-halogen" combustion agent: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2700g of cyclohexane, 740g of allyl diethyl phosphate, 260g of allyl bromide and 2.5g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 1.9g of TBHP when the temperature of the polymerization kettle reaches 65 ℃, reacting for 6.0hr, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.

(3) Preparation of grafted HIPS: 32g of toluene and 8g of TBHP are put into a beaker and mixed for 8min, the mixed liquid, 1000g of HIPS (492J) and 80g of Acrylic Acid (AA) are put into a 10L high-speed mixer together and mixed for 13min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 10min, the HIPS-g-AA graft (grafting rate 3.8%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 320g of macromolecular phosphorus-bromine flame retardant, 70g of HIPS-g-AA, 160g of functionalized kaolin, 10g of zinc stearate and 10106 g of antioxidant 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; and performing extrusion reaction for 5.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: adding 3800g of deionized water, 90g of sodium dodecyl benzene sulfonate and 480g of carboxylic styrene-butadiene latex into a 15L stainless steel polymerization kettle, adding 1000g of kaolin and NDZ-10145g when the temperature is raised to 58 ℃, stirring and mixing for 66min, adjusting the pH value of the system to 9.7 by using sodium hydroxide, then adding 45g of sodium oleate and 50g of magnesium sulfate, heating to 87 ℃, stirring for 18min for curing, and then dehydrating, drying and grinding to obtain the functionalized kaolin.

(2) Preparation of macromolecular "phosphorus-halogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for 2 times of replacement, sequentially adding 2900g of cyclohexane, 720g of allyl diethyl phosphate, 280g of allyl bromide and 2.9g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 2.2g of TBHP when the temperature of the polymerization kettle reaches 68 ℃, reacting for 6.5 hours, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.

(3) Preparation of grafted HIPS: putting 40g of toluene and 9g of TBHP into a beaker, mixing for 9min, putting the mixed liquid, 1000g of HIPS (492J) and 90g of Acrylic Acid (AA) into a 10L high-speed mixer, mixing for 14min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 11min, the HIPS-g-AA graft (grafting rate 4.4%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 360g of macromolecular phosphorus-bromine flame retardant, 90g of HIPS-g-AA, 180g of functionalized kaolin, 10g of zinc stearate and 10106 g of antioxidant into a 10L high-speed mixer to be mixed for 9min 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 6.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: 4000g of deionized water, 100g of sodium dodecyl benzene sulfonate and 500g of carboxylic styrene-butadiene latex are added into a 15L stainless steel polymerization kettle, 1000g of kaolin and NDZ-10150 g are added when the temperature is raised to 60 ℃, after stirring and mixing for 70min, the pH value of the system is adjusted to 10 by using sodium hydroxide, 50g of sodium oleate and 60g of magnesium sulfate are added, the mixture is stirred for 20min when the temperature is raised to 90 ℃ for curing, and then the functionalized kaolin is obtained through dehydration, drying and grinding.

(2) Preparation of macromolecular "phosphorus-halogen" 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 allyl chloride and 3.0g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 2.5g of TBHPH when the temperature of the polymerization kettle reaches 70 ℃, reacting for 7.0hr, washing and drying to obtain the macromolecular phosphorus-chlorine flame retardant.

(3) Preparation of grafted HIPS: 50g of toluene and 10g of TBHP are put into a beaker and mixed for 10min, the mixed liquid, 1000g of HIPS (492J) and 100g of Acrylic Acid (AA) are put into a 10L high-speed mixer together and mixed for 15min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 12min, the HIPS-g-AA graft (grafting rate 5.0%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 400g of macromolecular phosphorus-chlorine flame retardant, HIPS-g-AA100g, 200g of functionalized kaolin, 13g of zinc stearate and 10108 g of antioxidant 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; and performing extrusion reaction for 6.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: the same as in example 1.

(2) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 1.

(3) Preparation of grafted HIPS: the same as in example 1.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: the other conditions were the same as in example 1, except that the amount of the functionalized smoke suppressant added during the preparation of the high flame retardant, low smoke, high impact polystyrene resin was 50g, namely: putting 2000g of high impact polystyrene resin (492J), 200g of macromolecular phosphorus-bromine flame retardant, 20g of HIPS-g-AA, 50g of functionalized kaolin, 5g of stearic acid and 10103 g of antioxidant 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 high-flame-retardant, low-smoke and 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-halogen" flame retardant: the same as in example 2.

(2) Preparation of grafted HIPS: the same as in example 2.

(3) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: the other conditions were the same as in example 2, except that the functionalized kaolin was not added during the preparation of the high flame retardant, low smoke, high impact polystyrene resin, but the kaolin was directly added in an amount of 130g, that is: putting 2000g of high impact polystyrene resin (492J), 250g of macromolecular phosphorus-bromine flame retardant, 40g of HIPS-g-AA, 130g of kaolin, 6g of zinc stearate and 10104 g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 6 min; 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 4.5min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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) Preparing a functional smoke suppressant: the other conditions were the same as in example 3, except that the amount of the carboxylated styrene-butadiene latex added during the preparation of the functionalized smoke suppressant was 100g, namely: 3500g of deionized water, 70g of sodium dodecyl benzene sulfonate and 100g of carboxylic styrene-butadiene latex are added into a 15L stainless steel polymerization kettle, 1000g of kaolin and NDZ-10130 g are added when the temperature is raised to 55 ℃, after stirring and mixing for 60min, the pH value of the system is adjusted to 9.5 by using sodium hydroxide, 30g of sodium oleate and 40g of magnesium sulfate are added, the temperature is raised to 85 ℃, stirring for 15min is carried out for curing, and then dehydration, drying and grinding are carried out to obtain the functionalized kaolin-1.

(2) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 3.

(3) Preparation of grafted HIPS: the same as in example 3.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: the other conditions were the same as in example 3, except that the functionalized kaolin was not added during the preparation of the high flame retardant, low smoke, high impact polystyrene resin, but the functionalized kaolin-1 was added in an amount of 150g, namely: putting 2000g of high impact polystyrene resin (492J), 290g of macromolecular phosphorus-bromine flame retardant, 50g of HIPS-g-AA, 1150 g of functionalized kaolin, 8g of zinc stearate and 10105g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 7 min; 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 5.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: the same as in example 4.

(2) Preparation of grafted HIPS: the same as in example 4.

(3) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: the other conditions were the same as in example 4, except that the molecular "phosphorus-bromine" flame retardant was not increased during the preparation of the high flame retardant, low smoke, high impact polystyrene resin, only diethyl allylphosphate was added in an amount of 320g, i.e.: putting 2000g of high impact polystyrene resin (492J), 320g of allyl diethyl phosphate, 70g of HIPS-g-AA, 160g of functionalized kaolin, 10g of zinc stearate and 10106 g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 8 min; 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 5.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 smoke suppressant: the same as in example 5.

(2) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 5.

(3) Preparation of grafted HIPS: the other conditions were the same as in example 5, except that the amount of acrylic acid added during the preparation of the grafted HIPS was 20g, namely: 40g of toluene and 9g of TBHP are put into a beaker and mixed for 9min, the mixed liquid, 1000g of HIPS (492J) and 20g of Acrylic Acid (AA) are put into a 10L high-speed mixer together and mixed for 14min at high speed, 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: 170, 175, 180, 185, 190, 190, 200, 180, 170; after extrusion reaction for 11min, the HIPS-g-AA graft a (grafting rate of 1.2%) was obtained by extrusion, cooling and granulation.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: the other conditions were the same as in example 5, except that HIPS-g-AA graft was not added during the preparation of the high flame retardant, low smoke, high impact polystyrene resin, but HIPS-g-AA graft a was added in an amount of 90g, that is: putting 2000g of high impact polystyrene resin (492J), 360g of macromolecular phosphorus-bromine flame retardant, 90g of HIPS-g-AA graft a, 180g of functionalized kaolin, 10g of zinc stearate and 10106 g of antioxidant into a 10L high-speed mixer for high-speed mixing for 9 min; 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 6.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.

Comparative example 6

(1) Preparing a functional smoke suppressant: the same as in example 6.

(2) The macromolecule "phosphorus-halogen" is as in example 6.

(3) Preparation of grafted HIPS: the same as in example 6.

(4) Preparing high flame-retardant, low-smoke and high impact polystyrene resin: the other conditions were the same as in example 6 except that the amount of macromolecular "phosphorus-bromine" flame retardant added during the preparation of the high flame retardant, low smoke, high impact polystyrene resin was 100g, namely: putting 2000g of high impact polystyrene resin (492J), 100g of macromolecular phosphorus-chlorine flame retardant, 100g of bromoacylation HIPS, 200g of functionalized kaolin, 13g of zinc stearate and 10108 g of antioxidant into a 10L high-speed mixer, and mixing at high speed for 10 min; 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 6.0min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant, low-smoke and 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 highly flame-retardant, Low-Smoke, high-impact polystyrene resin

Reference sample^*: polystyrene (492J) commercially available from Yanshan petrochemical company, China petrochemical.