CN113402836A - Macromolecular phosphorus-halogen flame retardant modified high impact polystyrene resin composition and preparation method thereof - Google Patents
Macromolecular phosphorus-halogen flame retardant modified high impact polystyrene resin composition and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of high-flame-retardant high-impact polystyrene resin with an oxygen index of more than 36%. Firstly, synthesizing a macromolecular phosphorus-halogen flame retardant; secondly, preparing the halogenated and acylated HIPS by carrying out the halogenation reaction on the HIPS by using acid anhydride and a halogenating agent; and finally, directly blending and granulating the macromolecular phosphorus-halogen flame retardant, the halogen acylated HIPS and the high impact polystyrene resin to prepare the high flame-retardant high impact polystyrene resin. The method realizes the macro-molecular of the flame retardant, improves the compatibility of the macro-molecular flame retardant and the high impact polystyrene resin, solves the problems of migration, precipitation and uneven dispersion of the flame retardant in the high impact polystyrene resin adhesive matrix, and endows the high impact polystyrene resin with the characteristics of high flame retardancy, high efficiency, durability and the like.
Description
Technical Field
The invention relates to the field of high impact polystyrene resin modification, in particular to a preparation method of a macromolecular 'phosphorus-halogen' flame retardant modified high impact polystyrene resin.
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 development of novel efficient flame retardant materials becomes a hotspot of research.
In the prior art, the flame retardant research on high impact polystyrene resin is mainly to improve the flame retardancy of the product by adding a micromolecular inorganic flame retardant and a micromolecular organic flame retardant, namely dispersing a halogen compound, an inorganic powder flame retardant and the like in a high impact polystyrene resin material by a mechanical blending method. Such as: ZL200410086287.0 discloses a method for preparing a flame-retardant high impact polystyrene composition by adding halogen flame retardant decahalodiphenyl ether, auxiliary flame retardant antimony trioxide and powdered rubber into high impact polystyrene resin and performing melt blending. 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. In Liu Jian, deca-halogenated diphenyl ether, deca-halogenated diphenylethane halogen flame retardant and High Impact Polystyrene (HIPS) are blended to prepare weather-resistant flame-retardant HIPS resin with excellent flame retardant performance and weather resistance, wherein the influence of the halogen flame retardant on the weather resistance of the flame-retardant HIPS resin is shown (aging and application of synthetic materials, 2014,43(4): 13-15).
Although the methods disclosed in these patents and documents adopt small-molecule halogen flame retardants and small-molecule inorganic flame retardants to improve the flame retardant effect of the HIPS resin, these methods still have certain limitations, and these small-molecule flame retardants have the characteristics of short chain segment, high polarity and the like, cannot be tightly wound around the high-molecular chain segment of the nonpolar HIPS resin, have the problems of migration, precipitation and compatibility, and result in poor stability and durability of the flame retardant effect of the modified HIPS resin.
Disclosure of Invention
The invention aims to provide a preparation method of high-flame-retardant high-impact polystyrene resin with an oxygen index of more than 36%. Firstly, synthesizing a macromolecular phosphorus-halogen flame retardant; secondly, preparing the halogenated and acylated HIPS by carrying out the halogenation reaction on the HIPS by using acid anhydride and a halogenating agent; and finally, directly blending and granulating the macromolecular phosphorus-halogen flame retardant, the halogen acylated HIPS and the high impact polystyrene resin to prepare the high flame-retardant high impact polystyrene resin. The method realizes the macro-molecular of the flame retardant, improves the compatibility of the macro-molecular flame retardant and the high impact polystyrene resin, solves the problems of migration, precipitation and uneven dispersion of the flame retardant in the high impact polystyrene resin adhesive matrix, and endows the high impact polystyrene resin with the characteristics of high flame retardancy, high efficiency, durability and the like.
The "parts" in the present invention mean parts by mass.
The preparation of the high flame-retardant high impact polystyrene resin is carried out in a reaction kettle and a screw kneading machine, and the specific preparation steps are as follows:
(1) preparation of macromolecular "phosphorus-halogen" flame retardant: taking the total mass of allyl phosphate diester and allyl halide as 100 parts, 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 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 preparing the macromolecular phosphorus-halide flame retardant.
(2) Preparation of haloacylated HIPS: taking 100 parts of high impact polystyrene resin, firstly introducing inert gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 300-400 parts of solvent and 100 parts of HIPS (high impact polystyrene), heating to 40-60 ℃, stirring for dissolving for 2.0-3.0 hours, adding 10-15 parts of anhydride and 0.01-0.2 part of catalyst into the reaction kettle after the HIPS is completely dissolved, stirring for reaction for 1-4 hours, then adding 15-20 parts of halogenating agent, and dropwise adding 0.1-0.5 part of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 2-5), heating to 50-60 ℃, reacting for 5-10 hr, adding 5-10 parts of dilute hydrochloric acid water with the mass concentration of 1.5-5.0%The solution stops the reaction, and the halogenated acylated HIPS (the acylation degree is more than 2.0 percent, and the halogen content is more than 5mol percent) is prepared by suction filtration, washing and drying.
(3) Preparing high-flame-retardant high-impact polystyrene resin: taking 100 parts of high impact polystyrene resin, adding 100 parts of the high impact polystyrene resin, 10-20 parts of macromolecular phosphorus-halogen flame retardant, 1-5 parts of halogenated acylated HIPS, 0.2-0.6 part of stabilizer and 0.1-0.3 part of antioxidant into a high-speed mixer, and mixing at high speed for 5-10 min; 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 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 halide is one of allyl bromide and allyl chloride, and is preferably allyl 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 initiator is an organic peroxide selected from dicumyl peroxide, cumene hydroperoxide and Benzoyl Peroxide (BPO), preferably Benzoyl Peroxide (BPO).
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 acid anhydride is a binary acid anhydride compound, is selected from one of succinic anhydride, maleic anhydride and phthalic anhydride, and preferably is phthalic anhydride.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine.
The catalyst is selected from anhydrous aluminum trichloride (AlCl)3) Boron trifluoride (BF)3) Tin tetrachloride (SnCl)4) Zinc dichloride (ZnCl)2) Preferably AlCl3。
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 nitrogen or one of group 0 rare gases other than radon, preferably argon.
The solvent, antioxidant and stabilizer 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 invention firstly adopts micromolecular flame retardant allyl phosphodiester and allyl halide to carry out copolymerization to prepare macromolecular phosphorus-halogen flame retardant, which not only avoids the migration and precipitation of the micromolecular flame retardant in a high impact polystyrene resin matrix, improves the durability of the flame retardant effect, but also reduces the dosage of the halogen-containing flame retardant, and reduces the harm of a large amount of corrosive and toxic smoke gas generated by the halogen flame retardant during combustion to human bodies and the environment. And secondly, performing halogen acylation treatment on the HIPS, wherein the halogen-acylated HIPS plays a role of a coupling agent on the one hand, and because the polar group halogen atoms and acyl groups in the halogen-acylated HIPS can generate mutual attraction with ester groups and halogen atoms in the macromolecular phosphorus-halogen flame retardant, and in addition, the PS unit chain structure in the halogen-acylated HIPS is completely the same as that of the high impact polystyrene, the compatibility of the macromolecular phosphorus-halogen flame retardant and the high impact polystyrene resin can be obviously improved, the problem of uneven dispersion of the macromolecular phosphorus-halogen flame retardant in the high impact polystyrene resin matrix is solved, and the phosphorus-halogen synergistic flame retardant effect in the flame retardant is obviously enhanced. On the other hand, the halogen atoms of the flame-retardant group in the halogenated and acylated HIPS are embedded into the main chain of the HIPS polymer, so that the high-efficiency flame-retardant property of the high impact polystyrene resin is endowed. Therefore, the synergistic effect generated by the macromolecular phosphorus-halogen flame retardant and the halogen acylated HIPS ensures that the high impact polystyrene resin can obtain high flame retardant performance with oxygen index of more than 36 percent when the addition amount of the flame retardant is low, and the high impact polystyrene resin is higher than the national standard requirement of flame retardant plastics. The method has the characteristics of low addition proportion, good flame retardant effect and the like.
Firstly, raw material sources:
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.
Self-extinguishing time determination: the measurement was carried out according to the method described in UL-94.
Measurement of acylation degree: the test was carried out using an infrared spectrometer of Shimadzu, Japan, model IR-460.
And (3) determination of bromine content: the bromine content in the halogenated and acylated HIPS is measured by an alkali dissolution method and by AgNO3Titration of the standard solution, calibration of its concentration with the reference substance NaCl, eosin (C)20H6O5BrNa2) For the indicator, the end point solution was titrated from light red to light purple. The bromine content is calculated as follows:
in the formula: C-AgNO3The concentration of the standard solution; V-AgNO3The volume consumed by the standard solution; n-moles of acylating groups in the haloacylated HIPS; m-mass of HIPS (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) 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 reaction kettle, stirring, mixing and heating, adding 0.5g of BPO when the temperature of the reaction kettle reaches 50 ℃, reacting for 4.0hr, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.
(2) Preparation of haloacylated HIPS: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of dimethylbenzene and 1000g of HIPS into the reaction kettle, heating to 40 ℃, stirring for dissolving for 2.0 hours, and then adding 100g of phthalic anhydride and AlCl into the reaction kettle30.5g, stirring and reacting for 1.0hr, then adding 150g of liquid bromine, and dripping 1.0g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 2) heating to 50 deg.C, reacting for 5hr, adding 50g dilute hydrochloric acid (mass concentration is 1.5%) to terminate the reaction, filtering, washing, and drying to obtain bromoacylation HIPS (acylation degree is 2.7%, bromine content is 5.5 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 200g of macromolecular phosphorus-bromine flame retardant, 20g of bromoacylation HIPS, 4g of zinc stearate and 10102 g of antioxidant into a 10L high-speed mixer together, and mixing at high speed for 5 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 4min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of macromolecular "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 reaction kettle, stirring, mixing and heating, adding 0.9g of BPO when the temperature of the reaction kettle reaches 55 ℃, reacting for 4.5 hours, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.
(2) Preparation of haloacylated HIPS: firstly, argon is introduced into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, 3200g of dimethylbenzene and 1000g of HIPS are sequentially added into the reaction kettle, the temperature is raised to 45 ℃, stirring is carried out for dissolution for 2.3 hours, and then 110g of phthalic anhydride and AlCl are added into the reaction kettle30.7g, stirring and reacting for 1.5hr, then adding 160g of liquid bromine, and dripping 2.0g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 2) heating to 53 deg.C, reacting for 6hr, adding 60g dilute hydrochloric acid (mass concentration is 2.0%) to terminate the reaction, filtering, washing, and drying to obtain bromoacylation HIPS (acylation degree is 3.5%, bromine content is 6.1 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 240g of macromolecular phosphorus-bromine flame retardant, 40g of bromoacylation HIPS, 5g of zinc stearate and 10104 g of antioxidant into a 10L high-speed mixer together, 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 high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of macromolecular "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 reaction kettle, stirring, mixing and heating, adding 1.5g of BPO when the temperature of the reaction kettle reaches 60 ℃, reacting for 5.0hr, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.
(2) Preparation of haloacylated HIPS: firstly, argon is introduced into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, 3500g of dimethylbenzene and 1000g of HIPS are sequentially added into the reaction kettle, the temperature is raised to 50 ℃, stirring is carried out for dissolution for 2.5 hours, and then 120g of phthalic anhydride and AlCl are added into the reaction kettle31.1g, stirring and reacting for 2.0hr, then adding 170g of liquid bromine, and dripping 3.0g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 3) heating to 55 deg.C, reacting for 7hr, adding 70g dilute hydrochloric acid (mass concentration of 3.0%) to terminate the reaction, filtering, washing, and drying to obtain bromoacylation HIPS (acylation degree of 3.9%, bromine content of 7.2 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 280g of macromolecular phosphorus-bromine flame retardant, 50g of bromoacylation HIPS, 8g of zinc stearate and 10105 g of antioxidant into a 10L high-speed mixer together, 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 high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of macromolecular "phosphorus-halogen" flame retardant: 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 reaction kettle, stirring, mixing and heating, adding 1.9g of BPO when the temperature of the reaction kettle reaches 65 ℃, reacting for 6.0hr, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.
(2) Preparation of haloacylated HIPS: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3600g of dimethylbenzene and 1000g of HIPS into the reaction kettle, heating to 50 ℃, stirring for dissolving for 2.7 hours, and then adding 130g of phthalic anhydride and AlCl into the reaction kettle31.3g, stirring and reacting for 2.5hr, then adding 180g of liquid bromine, and dripping 3.5g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 3) heating to 57 deg.C, reacting for 8hr, adding 80g dilute hydrochloric acid (mass concentration is 3.5%) to terminate the reaction, filtering, washing, and drying to obtain bromoacylation HIPS (acylation degree is 4.2%, bromine content is 8.5 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 320g of macromolecular phosphorus-bromine flame retardant, 70g of bromoacylation HIPS, 10g of zinc stearate and 10106g of antioxidant into a 10L high-speed mixer together, 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 high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) 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 reaction kettle, stirring, mixing and heating, adding 2.2g of BPO when the temperature of the reaction kettle reaches 68 ℃, reacting for 6.5 hours, washing and drying to obtain the macromolecular phosphorus-bromine flame retardant.
(2) Preparation of haloacylated HIPS: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3800g of dimethylbenzene and 1000g of HIPS into the reaction kettle, heating to 55 ℃, stirring for dissolving for 2.9 hours, and then adding 140g of phthalic anhydride and AlCl into the reaction kettle31.7g, stirring and reacting for 3.0hr, and then190g of liquid bromine was added, and 4.5g of HCl-CH was added dropwise3OH solution (HCl: CH)3The molar ratio of OH is: 1: 4) heating to 59 deg.C, reacting for 9hr, adding 90g dilute hydrochloric acid (mass concentration of 4.5%) to terminate the reaction, filtering, washing, and drying to obtain bromoacylation HIPS (acylation degree of 4.9%, bromine content of 9.1 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 350g of macromolecular phosphorus-bromine flame retardant, 90g of bromoacylation HIPS, 10g of zinc stearate and 10106g of antioxidant into a 10L high-speed mixer together, and mixing at high speed 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 high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) 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 reaction kettle, stirring, mixing and heating, adding 2.5g of BPO2 when the temperature of the reaction kettle reaches 70 ℃, reacting for 7.0hr, washing and drying to obtain the macromolecular phosphorus-chlorine flame retardant.
(2) Preparation of haloacylated HIPS: firstly, argon is introduced into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, 4000g of dimethylbenzene and 1000g of HIPS are sequentially added into the reaction kettle, the temperature is raised to 60 ℃, stirring is carried out for dissolution for 3.0 hours, and then 150g of phthalic anhydride and AlCl are added into the reaction kettle32.0g, stirring and reacting for 3.0hr, then introducing 200g of chlorine gas, and dropwise adding 5.0g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 5) heating to 60 deg.C, reacting for 10hr, adding 100g dilute hydrochloric acid (mass concentration is 5.0%) to terminate the reaction, filtering, washing, and drying to obtain chlorinated HIPS (acylation degree is 5.2%, chlorine content is 9.5 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: putting 2000g of high impact polystyrene resin (492J), 00g of macromolecular phosphorus-chlorine flame retardant, 100g of chloridized HIPS, 15g of zinc stearate and 10107 g of antioxidant into a 10L high-speed mixer together, 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 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) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 1.
(2) Preparation of haloacylated HIPS: the same as in example 1.
(3) Preparing high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 1 except that 10g of bromoacylated HIPS was added during the preparation of the high flame retardant high impact polystyrene resin, namely: putting 2000g of high impact polystyrene resin (492J), 200g of macromolecular phosphorus-bromine flame retardant, 10g of bromoacylation HIPS, 4g of zinc stearate and 10102 g of antioxidant into a 10L high-speed mixer together, and mixing at high speed for 5 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 4min, and then performing extrusion, cooling and granulation to obtain the high-flame-retardant high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of haloacylated HIPS: the same as in example 2.
(2) Preparing high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 2, except that the molecular "phosphorus-bromine" flame retardant was not increased during the preparation of the highly flame-retardant high impact polystyrene resin, and only diethyl allylphosphate was added in an amount of 240g, namely: putting 2000g of high impact polystyrene resin (492J), 240g of diethyl allylphosphate, 40g of bromoacylation HIPS, 5g of zinc stearate and 10104 g of antioxidant into a 10L high-speed mixer together, 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 high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of haloacylated HIPS: the same as in example 3.
(2) Preparing high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 3, except that the molecular "phosphorus-bromine" flame retardant was not increased during the preparation of the high flame-retardant high impact polystyrene resin, and only allyl bromide was added in an amount of 280g, that is: putting 2000g of high impact polystyrene resin (492J), 280g of allyl bromide, 50g of bromoacylation HIPS, 8g of zinc stearate and 10105 g 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 high-impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 4.
(2) Preparation of haloacylated HIPS: the same as in example 4.
(3) Preparing high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 4 except that the amount of the macromolecular "phosphorus-bromine" flame retardant added during the preparation of the high flame-retardant high impact polystyrene resin was 50g, namely: putting 2000g of high impact polystyrene resin (492J), 50g of macromolecular phosphorus-bromine composite flame retardant, 70g of bromoacylation HIPS, 10g of zinc stearate and 10106g of antioxidant into a 10L high-speed mixer together, 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 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) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 5.
(2) Preparation of haloacylated HIPS: the other conditions were the same as in example 5 except that the amount of phthalic anhydride added during the preparation of the haloacylated HIPS was 70g, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3800g of dimethylbenzene and 1000g of HIPS into the reaction kettle, heating to 55 ℃, stirring for dissolving for 2.9 hours, and then adding 70g of phthalic anhydride and AlCl into the reaction kettle31.7g, stirring and reacting for 3.0hr, then adding 190g of liquid bromine, and dropwise adding 4.5g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 4) heating to 59 deg.C, reacting for 9hr, adding 90g dilute hydrochloric acid (mass concentration is 4.5%) to terminate the reaction, filtering, washing, and drying to obtain bromoacylation HIPS-1 (acylation degree is 1.9%, bromine content is 6.7 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 5 except that no bromoacylated HIPS was added during the preparation of the high flame retardant high impact polystyrene resin, and bromoacylated HIPS-1 was added in an amount of 90g, namely: putting 2000g of high impact polystyrene resin (492J), 350g of macromolecular phosphorus-bromine flame retardant, 190g of bromoacylation HIPS, 10g of zinc stearate and 10106g of antioxidant into a 10L high-speed mixer together, and mixing at high speed 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 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) Preparation of macromolecular "phosphorus-halogen" flame retardant: the same as in example 6.
(2) Preparation of haloacylated HIPS: except that the amount of chlorine added during the preparation of the haloacylated HIPS was 100g, i.e.: firstly, argon is introduced into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, 4000g of dimethylbenzene and 1000g of HIPS are sequentially added into the reaction kettle, the temperature is raised to 60 ℃, stirring is carried out for dissolution for 3.0 hours, and then 150g of phthalic anhydride and AlCl are added into the reaction kettle32.0g, stirring and reacting for 3.0hr, then introducing 100g of chlorine gas, and dropwise adding 5.0g of HCl-CH3OH solution (HCl: CH)3The molar ratio of OH is: 1: 5) heating to 60 deg.C, reacting for 10hr, adding 100g dilute hydrochloric acid (mass concentration is 5.0%) to terminate the reaction, filtering, washing, and drying to obtain chlorinated HIPS-2 (acylation degree is 5.0%, chlorine content is 4.7 mol%).
(3) Preparing high-flame-retardant high-impact polystyrene resin: the other conditions were the same as in example 6 except that no bromoacylated HIPS was added during the preparation of the high flame retardant high impact polystyrene resin, and bromoacylated HIPS-2 was added in an amount of 100g, namely: putting 2000g of high impact polystyrene resin (492J), 400g of macromolecular phosphorus-bromine flame retardant, 2100 g of chloridized HIPS, 15g of zinc stearate and 10107 g of antioxidant into a 10L high-speed mixer together, 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 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, high impact polystyrene resin
Reference sample*: is commercially availablePolystyrene (492J) manufactured by petrifaction Yanshan petrochemical company, China.
Claims (21)
1. A high flame retardant 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 halogen acylated high impact polystyrene; (4) 0.2-0.6 part of a stabilizer; (5) 0.1-0.3 part of antioxidant, which is characterized in that:
the molecular chain of the halogen acylated high impact polystyrene contains halogen elements and acyl;
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 high flame retardant high impact polystyrene resin composition of claim 1, wherein the 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. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 1, characterized by the following preparation steps:
(1) 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 halide and 0.1-0.5 part of molecular weight regulator into the reaction kettle, and stirring, mixing and heating the mixture, wherein the total mass of the allyl phosphate diester and the allyl halide is 100 parts;
(2) and adding 0.05-0.3 part of initiator when the temperature of the reaction kettle reaches 50-70 ℃, reacting for 4.0-7.0 hours, washing and drying after the reaction is finished, and thus obtaining the macromolecular phosphorus-halogen flame retardant.
4. A method of preparing a macromolecular phosphorus-halogen flame retardant according to claim 3, 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.
5. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 4, characterized in that said diallyl phosphate is diethyl allylphosphate.
6. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 3, wherein said allylic halide is one of allylic bromide and allylic chloride.
7. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 6, characterized in that the allylic halide is allylic bromide.
8. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 3, wherein said initiator is an organic peroxide selected from the group consisting of dicumyl peroxide, cumene hydroperoxide and benzoyl peroxide.
9. A process for preparing a macromolecular phosphorus-halogen flame retardant according to claim 8, characterized in that said initiator is benzoyl peroxide.
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 10, characterized in that said molecular weight regulator is tert-dodecyl mercaptan.
12. A process for the preparation of a halogen acylated high impact polystyrene as claimed in claim 1, characterized in that the preparation process comprises: taking 100 parts of high impact polystyrene resin, sequentially adding 300-400 parts of solvent and 100 parts of high impact polystyrene into a reaction kettle subjected to inert gas replacement, heating to 40-60 ℃, stirring and dissolving for 2.0-3.0 hr, adding 10-15 parts of anhydride and 0.01-0.2 part of catalyst into the reaction kettle after the high impact polystyrene is completely dissolved, stirring and reacting for 1-4 hr, then adding 15-20 parts of halogenating agent, and dropwise adding 0.1-0.5 part of HCl-CH3And (3) heating the OH solution to 50-60 ℃, reacting for 5-10 hours, adding 5-10 parts of dilute hydrochloric acid aqueous solution with the mass concentration of 1.5-5.0% to terminate the reaction, and performing suction filtration, washing and drying to obtain the halogen acylated high impact polystyrene.
13. The method of claim 12, wherein the acid anhydride is a dibasic acid anhydride compound selected from the group consisting of succinic anhydride, maleic anhydride, and phthalic anhydride.
14. The process for preparing a haloacylated high impact polystyrene as claimed in claim 13, wherein the anhydride is phthalic anhydride.
15. The process for preparing a haloacylated high impact polystyrene as claimed in claim 12 wherein the halogenating agent is one of liquid chlorine and liquid bromine.
16. The process for preparing a haloacylated high impact polystyrene as claimed in claim 15, wherein the halogenating agent is liquid bromine.
17. The process for preparing a haloacylated high impact polystyrene as claimed in claim 12, wherein the catalyst is selected from one of anhydrous aluminum trichloride, boron trifluoride, tin tetrachloride and zinc dichloride.
18. The process for preparing a haloacylated high impact polystyrene as claimed in claim 17, wherein the catalyst is aluminum trichloride.
19. A method for preparing the high flame retardant high impact polystyrene resin composition as defined in claim 1, which is characterized by comprising the steps of: 100 parts of high impact polystyrene resin, 10-20 parts of macromolecular phosphorus-halogen flame retardant, 1-5 parts of halogen acylated high impact polystyrene, 0.2-0.6 part of stabilizer and 0.1-0.3 part of antioxidant are uniformly mixed by taking 100 parts of high impact polystyrene resin as a raw material, then the mixed material is directly added into a screw kneading machine, the reaction temperature is 160-200 ℃, and the high flame retardant high impact polystyrene resin is obtained after reaction, extrusion, cooling and granulation.
20. The method for preparing a highly flame retardant high impact polystyrene resin composition as claimed in claim 19, wherein said screw kneader is selected from the group consisting of a single screw extruder and a multi-screw extruder.
21. The method for preparing a high flame retardant high impact polystyrene resin composition as claimed in claim 20, wherein said screw kneader is a twin-screw extruder.
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