CN113429725B - Preparation method of environment-friendly high-molecular phosphorus-nitrogen flame retardant modified high impact polystyrene - Google Patents
Preparation method of environment-friendly high-molecular phosphorus-nitrogen flame retardant modified high impact polystyrene Download PDFInfo
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Abstract
The invention provides a preparation method of environment-friendly flame-retardant high impact polystyrene resin with oxygen index of more than 40 percent. Firstly, synthesizing a macromolecular phosphorus-nitrogen flame retardant with reactivity by using a micromolecular flame retardant, namely allyl phosphodiester, N-allylaniline and 1, 3-butadiene; secondly, styrene and macromolecular phosphorus-nitrogen flame retardant with reaction activity are copolymerized to prepare macromolecular phosphorus-nitrogen flame retardant; finally, directly blending and granulating the high-molecular phosphorus-nitrogen flame retardant and the high impact polystyrene resin to prepare the environment-friendly flame-retardant high impact polystyrene resin. The method realizes the high polymerization of the flame retardant, directly realizes the mutual compatibility of the flame retardant and the high impact polystyrene resin, and endows the high impact polystyrene resin with the characteristics of environmental protection, high efficiency and durability of flame retardant property. The method has the characteristics of environmental protection, low addition proportion, good flame retardant effect, low modification cost and the like.
Description
Technical Field
The invention relates to a preparation method of environment-friendly flame-retardant high impact polystyrene resin, in particular to a preparation method of high impact polystyrene resin flame-retardant modified by a high-molecular phosphorus-nitrogen flame retardant.
Background
High Impact Polystyrene (HIPS) is an important styrene resin material developed on the basis of general polystyrene materials, has the advantages of good rigidity, processability, colorability and the like of the general polystyrene, has greatly improved impact strength, and has wide application in various fields such as packaging, disposable products, appliances, consumer appliances, toys, building products, ornaments and the like at present. However, HIPS, which is a common disadvantage of general polymer materials, also has problems such as easy combustion and rapid flame propagation during combustion, and its application is greatly limited in environments with high temperature requirements. At present, nearly 80% of fire retardants used in China are halogen-containing fire retardants, but in recent years, halogen-containing fire retardants generate a large amount of smoke, dioxin, corrosive gas and other problems during combustion, and cannot meet the requirement that European Union issues' directive (ROHS for short) about prohibition of use of certain harmful substances in electronic and electrical equipment in 2003, so that domestic electric appliances from China will be rejected by the European Union market. Therefore, china must develop halogen-free flame retardant materials vigorously to adapt to the development trend of the international market.
In the prior art, the research on halogen-free flame retardant of high impact polystyrene resin is mainly prepared by adding inorganic and organic halogen-free flame retardants. Such as: ZL96116942.7 discloses an environment-friendly flame-retardant rubber floor with low smoke, low toxicity and good flame retardant property, which is prepared by mutually matching halogen-free flame retardant aluminum hydroxide (magnesium), antimony trioxide and phosphorus flame retardant and by a mixing and blending process. ZL201110098731.0 discloses a magnesium hydroxide flame retardant subjected to surface treatment of sulfonated high impact polystyrene, which is mixed with high impact polystyrene resin to prepare a magnesium hydroxide flame retardant with impact strength of 5.4kJ/m 2 And the oxygen index is 29 percent. CN 111518355A discloses a method for preparing a flame-retardant high impact polystyrene composite material by using silane coupling agent modified phosphorus flame retardant ammonium polyphosphate and a nano flame retardant carbon nano tube.
The patents adopt small-molecule organic and inorganic powder halogen-free flame retardants for modification, and although obvious effects are achieved in the aspect of improving the flame retardance of HIPS resin, the small-molecule halogen-free flame retardants have far difference in surface properties from the HIPS resin, have different interfacial functions, and have the problems of migration, precipitation, low compatibility and low flame retardant efficiency with the HIPS, so that the flame retardants are large in dosage and poor in stability and durability.
Disclosure of Invention
The invention aims to provide a preparation method of environment-friendly flame-retardant high impact polystyrene resin with an oxygen index of more than 40%. Firstly, synthesizing a macromolecular phosphorus-nitrogen flame retardant with reactivity through a micromolecular flame retardant allyl phosphodiester, N-allylaniline and 1, 3-butadiene; secondly, styrene and macromolecular phosphorus-nitrogen flame retardant with reaction activity are copolymerized to prepare macromolecular phosphorus-nitrogen flame retardant; finally, directly blending and granulating the high-molecular phosphorus-nitrogen flame retardant and the high impact polystyrene resin to prepare the environment-friendly flame-retardant high impact polystyrene resin. The method realizes the high polymerization of the flame retardant, directly realizes the mutual compatibility of the flame retardant and the high impact polystyrene resin, and endows the high impact polystyrene resin with the characteristics of environmental protection, high efficiency and durability of flame retardant property.
The "parts" in the present invention mean parts by mass.
The preparation of the environment-friendly flame-retardant high impact polystyrene resin is carried out in a reaction kettle and a screw kneading machine, and the preparation steps are as follows:
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: based on 100 parts of total mass of allyl phosphodiester and N-allylaniline, firstly introducing nitrogen 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 phosphodiester, 20-30 parts of N-allylaniline and 0.1-0.5 part of molecular weight regulator into the polymerization kettle, stirring, mixing and heating, adding 0.05-0.5 part of initiator when the temperature of the polymerization kettle reaches 60-70 ℃, reacting for 5.0-7.0 hr, then adding 1.0-5.0 parts of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 40-60 min until no free monomer exists, washing and drying to prepare the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
(2) Preparation of high-molecular 'phosphorus-nitrogen' flame retardant: based on 100 parts of the total mass of the macromolecular phosphorus-nitrogen flame retardant, firstly introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 100 parts of macromolecular phosphorus-nitrogen flame retardant and 20-30 parts of styrene into a polymerization kettle, adding 0.3-0.6 part of initiator when the temperature is raised to 60-70 ℃, reacting for 4.0-6.0 hr, and adding 1.0-5.0 parts of terminator to prepare the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: based on 100 parts of high impact polystyrene resin, adding 100 parts of high impact polystyrene resin, 10-20 parts of high molecular phosphorus-nitrogen flame retardant, 0.2-0.6 part of stabilizer and 0.1-0.5 part of antioxidant into a high-speed mixer, mixing at high speed for 5-10 min, then directly adding the mixed materials into a double-screw extruder, reacting at the temperature of 160-200 ℃ for 4-6 min, extruding, cooling and granulating to obtain the environment-friendly flame-retardant high impact polystyrene resin.
The macromolecular phosphorus-nitrogen flame retardant has the following structural general formula:
in the formula: r is C 1 ～C 8 Alkyl groups of (a); PS is a homopolymer of styrene; b is an oligomer of 1, 3-butadiene. The allyl phosphate diester is one of allyl dimethyl phosphate, allyl diethyl phosphate, allyl dipropyl phosphate, allyl dibutyl phosphate, allyl dipentyl phosphate, allyl dihexyl phosphate, allyl diheptyl phosphate and allyl dioctyl phosphate, and preferably is allyl diethyl phosphate.
The high impact polystyrene is a copolymer (HIPS) of styrene and polybutadiene rubber, can be powder or granular resin, and has Melt Flow Rate (MFR) of 0.5-20 g/10min.
The initiator is an organic peroxide, is selected from one of dicumyl peroxide, cumene hydroperoxide, benzoyl Peroxide (BPO) and di-tert-butyl peroxide, and is 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 terminator is selected from one of methanol, ethanol, propanol and butanol.
The screw kneader according to the invention can be a single-screw extruder or a multi-screw extruder, preferably a twin-screw extruder.
The nitrogen and argon used as the replacement gas of the polymerizer in the present invention may be replaced with one of other group 0 rare gases other than radon.
The solvent, antioxidant 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 antioxidant. The stabilizer is stearate, such as zinc stearate or calcium stearate.
The invention firstly adopts micromolecule flame retardant allyl phosphodiester and N-allylaniline to carry out copolymerization to prepare the macromolecular phosphorus-nitrogen flame retardant, the macromolecular flame retardant not only improves the synergistic effect of the phosphorus-nitrogen flame retardant, but also avoids the migration and precipitation of the micromolecule flame retardant in a high impact polystyrene resin matrix, improves the high efficiency and the durability of the flame retardant effect, simultaneously does not contain halogen flame retardant, and avoids the harm of a large amount of corrosive and toxic smoke gas to human bodies and environment caused by the halogen flame retardant during combustion. Secondly, 1, 3-butadiene is used for carrying out end-capping activation treatment on the macromolecular phosphorus-nitrogen flame retardant to ensure that the macromolecular phosphorus-nitrogen flame retardant has reaction activity and can carry out copolymerization reaction with styrene so as to ensure that the macromolecular phosphorus-nitrogen flame retardant and [ -PS-] L Form block copolymer to form high molecular phosphorus-nitrogen fire retardant. The PS unit chain structure in the macromolecular phosphorus-nitrogen flame retardant is the same as the styrene chain structure in the high impact polystyrene, the compatibility of the macromolecular phosphorus-nitrogen flame retardant and the high impact polystyrene resin can be obviously improved, the problem that the macromolecular phosphorus-nitrogen flame retardant is dispersed in the high impact polystyrene resin matrix is effectively solved, the phosphorus-nitrogen synergistic effect in the macromolecular flame retardant is obviously enhanced, the high flame retardant performance can be obtained, and the high flame retardant high impact polystyrene resin with the oxygen index of more than 40 percent and far higher than the national standard requirement of flame retardant plastics can be prepared. The method has the characteristics of environmental protection, low modification cost, high flame retardant efficiency and the like.
Detailed Description
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The "parts" described in examples and comparative examples each refer to parts by mass.
The method comprises the following steps of raw material sources:
other reagents are all commercial products
Analysis and test method:
determination of oxygen index: the assay was carried out as described in GB 10707-1989.
Measurement by vertical Combustion method: the assay was carried out as described in GB/T13488-1992.
And (3) measuring self-extinguishing time: the measurement was carried out according to the method described in UL-94.
Device and instrument for performing the following steps
Phi 34 twin-screw extruder Long/diameter =34/1 Lestreiz Germany
10L high-speed mixer Fuxin Plastic 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-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of cyclohexane, 700g of allyl diethyl phosphate, 300g of N-allyl aniline and 1g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 0.5g of BPO when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.0hr, then adding 10g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 40min, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
(2) Preparation of high-molecular 'phosphorus-nitrogen' flame retardant: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of cyclohexane, 1000g of macromolecular phosphorus-nitrogen flame retardant and 200g of styrene into the polymerization kettle, heating to 60 ℃, adding 3.0g of BPO, reacting for 4.0hr, and then adding 10g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 200g of high-molecular phosphorus-nitrogen flame retardant, 4g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together, mixing 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 environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for 2 times of replacement, sequentially adding 2300g of cyclohexane, 730g of allyl diethyl phosphate, 270g of N-allyl aniline and 2g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing, heating, adding 1.0g of BPO1 when the temperature of the polymerization kettle reaches 62 ℃, reacting for 5.5 hours, then adding 20g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 45 minutes, washing and drying to obtain the macromolecular 'phosphorus-nitrogen' flame retardant with reaction activity.
(2) Preparation of high-molecular 'phosphorus-nitrogen' flame retardant: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2300g of cyclohexane, 1000g of macromolecular phosphorus-nitrogen flame retardant and 220g of styrene into the polymerization kettle, heating to 63 ℃, adding 4.0g of BPO, reacting for 4.5 hours, and then adding 20g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 240g of high-molecular phosphorus-nitrogen flame retardant, 6g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together, mixing for 6min at a high speed, and finally adding the mixed material into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 4min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for 3 times, adding 2500g of cyclohexane, 750g of allyl diethyl phosphate, 250g of N-allyl aniline and 3g of tert-dodecyl mercaptan into the polymerization kettle in sequence, stirring, mixing, heating, adding 2.0g of BPO2 when the temperature of the polymerization kettle reaches 64 ℃, reacting for 6.0hr, adding 30g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50min, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2500g of cyclohexane, 1000g of macromolecular phosphorus-nitrogen flame retardant and 250g of styrene into the polymerization kettle, heating to 65 ℃, adding 4.5g of BPO, reacting for 5.0hr, and then adding 30g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 260g of high-molecular phosphorus-nitrogen flame retardant, 7g of zinc stearate and 1010 5g of antioxidant into a 10L high-speed mixer, mixing for 7min at a high speed, and finally adding the mixed material into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 5min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for 3 times, adding 2600g of cyclohexane, 770g of allyl diethyl phosphate, 230g of N-allyl aniline and 4g of tert-dodecyl mercaptan into the polymerization kettle in sequence, stirring, mixing and heating, adding 3.0g of BPO3 when the temperature of the polymerization kettle reaches 66 ℃, reacting for 6.3 hours, adding 35g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 53 minutes, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2700g of cyclohexane, 1000g of macromolecular phosphorus-nitrogen flame retardant and 270g of styrene into a polymerization kettle, heating to 67 ℃, adding 5.0g of BPO, reacting for 5.5 hours, and then adding 40g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 280g of high-molecular phosphorus-nitrogen flame retardant, 8g of zinc stearate and 1010 6g of antioxidant into a 10L high-speed mixer, mixing for 8min at a high speed, and finally adding the mixed material into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 5min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 2800g of cyclohexane, 780g of allyl diethyl phosphate, 220g of N-allyl aniline and 4g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 4.0g of BPO4 when the temperature of the polymerization kettle reaches 68 ℃, reacting for 6.5 hours, adding 40g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 55 minutes, washing and drying to prepare the macromolecular 'phosphorus-nitrogen' flame retardant with reaction activity.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 2900g of cyclohexane, 1000g of macromolecular phosphorus-nitrogen flame retardant and 290g of styrene into the polymerization kettle, heating to 69 ℃, adding 5.5g of BPO, reacting for 5.5 hours, and then adding 45g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 290g of high-molecular phosphorus-nitrogen flame retardant, 9g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer, mixing 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 6min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of cyclohexane, 800g of allyl diethyl phosphate, 200g of N-allylaniline and 5g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 5.0g of BPO5 when the temperature of the polymerization kettle reaches 70 ℃, reacting for 7.0hr, then adding 50g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 60min, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 3000g of cyclohexane, 1000g of macromolecular phosphorus-nitrogen flame retardant and 300g of styrene into a polymerization kettle, heating to 70 ℃, adding 6.0g of BPO, reacting for 6.0hr, and then adding 50g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: putting 2000g of HIPS (492J), 300g of high-molecular phosphorus-nitrogen flame retardant, 10g of zinc stearate and 1010 8g of antioxidant into a 10L high-speed mixer together, mixing at high speed for 10min, finally adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 6min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the same as in example 1.
(2) Preparation of high-molecular 'phosphorus-nitrogen' flame retardant: the same as in example 1.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: the other conditions are the same as example 1, except that the addition amount of the polymeric phosphorus-nitrogen flame retardant in the preparation process of the environment-friendly flame-retardant high impact polystyrene resin is 150g, namely: putting 2000g of HIPS (492J), 150g of high-molecular phosphorus-nitrogen flame retardant, 4g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together, mixing 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; after extrusion reaction for 4min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the same as in example 2.
(2) Preparation of environment-friendly flame-retardant high impact polystyrene resin: the other conditions are the same as example 2, except that the macromolecular "phosphorus-nitrogen" flame retardant is added during the preparation of the environment-friendly flame-retardant high impact polystyrene resin, and the addition amount is 240g, namely: putting 2000g of HIPS (492J), 240g of macromolecular phosphorus-nitrogen flame retardant, 6g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together, mixing for 6min at a high speed, and finally adding the mixed material into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 4min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: the other conditions were the same as in example 3, except that no N-allylaniline was added during the preparation of the macromolecular "phosphorus-nitrogen" flame retardant, i.e.: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2500g of cyclohexane, 750g of allyl diethyl phosphate and 3g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 2.0g of BPO2 when the temperature of the polymerization kettle reaches 64 ℃, reacting for 6.0hr, then adding 30g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50min, washing and drying to obtain the macromolecular 'phosphorus' flame retardant with reaction activity.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant: the other conditions were the same as in example 3, except that the macromolecular "phosphorus-nitrogen" flame retardant was added in an amount of 1000g instead of being added during the preparation of the macromolecular "phosphorus-nitrogen" flame retardant, namely: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2500g of cyclohexane, 1000g of macromolecular phosphorus flame retardant and 250g of styrene into the polymerization kettle, heating to 65 ℃, adding 4.5g of BPO, reacting for 5.0hr, and then adding 30g of methanol to terminate the reaction, thus obtaining the macromolecular phosphorus flame retardant.
(3) Preparation of environment-friendly flame-retardant high impact polystyrene resin: the other conditions are the same as those in example 3, except that the macromolecular phosphorus-nitrogen flame retardant is not added in the preparation process of the environment-friendly flame-retardant high impact polystyrene resin, and the addition amount is 260g, namely: putting 2000g of HIPS (492J), 260g of high-molecular phosphorus flame retardant, 7g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together for high-speed mixing for 7min, finally adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 5min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of high-molecular 'phosphorus-nitrogen' flame retardant: the other conditions were the same as in example 4, except that the macromolecular "phosphorus-nitrogen" flame retardant was prepared without adding the macromolecular "phosphorus-nitrogen" flame retardant, but with the addition of only 1000g of N-allylaniline, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2700g of cyclohexane, 1000g of N-allylaniline and 270g of styrene into the polymerization kettle, heating to 67 ℃, adding 5.0g of BPO, reacting for 5.5 hours, and then adding 40g of methanol to terminate the reaction, thereby obtaining the high molecular nitrogen flame retardant.
(2) Preparation of environment-friendly flame-retardant high impact polystyrene resin: the other conditions are the same as example 4, except that no macromolecular "phosphorus-nitrogen" flame retardant is added in the preparation process of the environment-friendly flame-retardant high impact polystyrene resin, and the addition amount is 280g, namely: putting 2000g of HIPS (492J), 280g of high molecular nitrogen flame retardant, 8g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer together for high-speed mixing for 8min, finally adding the mixed materials into a phi 34 twin-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 5min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Preparation of high molecular phosphorus-nitrogen flame retardant: the other conditions were the same as in example 4, except that the macromolecular "phosphorus-nitrogen" flame retardant was not added during the preparation of the macromolecular "phosphorus-nitrogen" flame retardant, but only diethyl allylphosphate was added in an amount of 1000g, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, adding 2900g of cyclohexane, 1000g of allyl diethyl phosphate and 290g of styrene into the polymerization kettle in sequence, heating to 69 ℃, adding 5.5g of BPO, reacting for 5.5 hours, and adding 45g of methanol to terminate the reaction, thereby obtaining the high molecular phosphorus flame retardant.
(2) Preparation of environment-friendly flame-retardant high impact polystyrene resin: the other conditions are the same as example 5, except that the macromolecular phosphorus flame retardant is added instead of the macromolecular phosphorus-nitrogen flame retardant in the preparation process of the environment-friendly flame-retardant high impact polystyrene resin, wherein the addition amount is 290g, namely: putting 2000g of HIPS (492J), 290g of high-molecular phosphorus flame retardant, 9g of zinc stearate and 1010 g of antioxidant into a 10L high-speed mixer, mixing for 9min at high speed, and finally adding the mixed material into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160 170, 180, 185, 190, 200, 195, 185, 175; after extrusion reaction for 6min, extrusion, cooling and granulation are carried out to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
Preparation of environment-friendly flame-retardant high impact polystyrene resin: the other conditions are the same as example 6, except that no high molecular phosphorus-nitrogen flame retardant is added in the preparation process of the environment-friendly flame-retardant high impact polystyrene resin, but allyl diethyl phosphate is directly added, the addition amount is 300g, namely: putting 2000g of HIPS (492J), 300g of allyl diethyl phosphate, 10g of zinc stearate and 1010 8g of antioxidant into a 10L high-speed mixer together, mixing at high speed for 10min, 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 6min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of Environment-friendly flame-retardant high impact polystyrene resin
Reference sample * : the polystyrene (492J) is commercially available from Yanshan petrochemical company, china petrochemical company.
Claims (12)
1. An environment-friendly flame-retardant high impact polystyrene resin composition comprises the following components in parts by mass: 100 parts of high impact polystyrene resin; (2) 10 to 20 parts of high-molecular phosphorus-nitrogen flame retardant; (3) 0.2 to 0.6 part of a stabilizer; (4) 0.1 to 0.5 part of antioxidant, which is characterized in that:
the structural general formula of the macromolecular phosphorus-nitrogen flame retardant is as follows:
in the formula: r is C 1 ～C 8 PS is a homopolymer of styrene; b is an oligomer segment of 1, 3-butadiene, m, n and L are the number of repeating units;
the preparation method of the macromolecular phosphorus-nitrogen flame retardant comprises the following steps:
(1) Preparation of macromolecular "phosphorus-nitrogen" flame retardant: taking the total mass of allyl phosphodiester and N-allylaniline as 100 parts, sequentially adding 200 to 300 parts of solvent, 70 to 80 parts of allyl phosphodiester, 20 to 30 parts of N-allylaniline and 0.1 to 0.5 part of molecular weight regulator into a polymerization kettle which is subjected to inert gas replacement, stirring, mixing and heating, adding 0.05 to 0.5 part of initiator when the temperature of the polymerization kettle reaches 60 to 70 ℃, reacting for 5.0 to 7.0 hours, then adding 1.0 to 5.0 parts of 1, 3-butadiene into the polymerization kettle, carrying out end capping, reacting for 40 to 60min until no free monomer exists, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity;
(2) Preparing a high-molecular phosphorus-nitrogen flame retardant: and (2) adding 200 to 300 parts of solvent, 100 parts of macromolecular phosphorus-nitrogen flame retardant and 20 to 30 parts of styrene into a polymerization kettle which is subjected to inert gas replacement in sequence by taking the total mass of the macromolecular phosphorus-nitrogen flame retardant as 100 parts, adding 0.3 to 0.6 part of initiator when the temperature is raised to 60 to 70 ℃, reacting for 4.0 to 6.0 hours, and adding 1.0 to 5.0 parts of terminator to prepare the high-molecular phosphorus-nitrogen flame retardant.
2. The environment-friendly flame-retardant high impact polystyrene resin composition according to claim 1, wherein the high impact polystyrene resin is a copolymer of styrene and polybutadiene rubber, and the melt flow rate is 0.5-20 g/10min.
3. The environmentally friendly flame retardant high impact polystyrene resin composition of claim 1, wherein the 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.
4. The environment-friendly flame retardant high impact polystyrene resin composition of claim 3, wherein said diallyl phosphate is diethyl allyl phosphate.
5. The environment-friendly flame-retardant high impact polystyrene resin composition as claimed in claim 1, wherein the molecular weight modifier is one selected from the group consisting of tertiary decamercaptan, tertiary dodecanethiol, tertiary tetradecanethiol and tertiary hexadecanethiol.
6. The environment-friendly flame retardant high impact polystyrene resin composition of claim 5, wherein said molecular weight regulator is t-dodecyl mercaptan.
7. The environment-friendly flame-retardant high impact polystyrene resin composition as claimed in claim 1, wherein said initiator is an organic peroxide selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide and di-t-butyl peroxide.
8. The environment-friendly flame-retardant high impact polystyrene resin composition according to claim 7, wherein the initiator is benzoyl peroxide.
9. The environment-friendly flame-retardant high impact polystyrene resin composition according to claim 1, wherein the terminator is one selected from methanol, ethanol, propanol and butanol.
10. A method for preparing the environment-friendly flame-retardant high impact polystyrene resin composition as claimed in claim 1, which is characterized in that the preparation process comprises: taking 100 parts of high impact polystyrene resin as 100 parts, fully mixing 100 parts of high impact polystyrene resin, 10 to 20 parts of high molecular phosphorus-nitrogen flame retardant, 0.2 to 0.6 part of stabilizer and 0.1 to 0.5 part of antioxidant, directly adding the mixture into a screw kneading machine, reacting at the temperature of 160 to 200 ℃, extruding through reaction, cooling, and granulating to obtain the environment-friendly flame-retardant high impact polystyrene resin.
11. The method for preparing an environmentally friendly flame retardant high impact polystyrene resin composition as claimed in claim 10, wherein said screw kneader is selected from a single screw extruder or a multi-screw extruder.
12. The method for preparing an environment-friendly flame retardant high impact polystyrene resin composition as claimed in claim 11, wherein said screw kneader is a twin-screw extruder.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0354034A2 (en) * | 1988-08-03 | 1990-02-07 | Toray Industries, Inc. | Resin composition |
| CN105694331A (en) * | 2013-07-30 | 2016-06-22 | 江苏理工学院 | Method for preparing halogen-free flame-retardant high-impact polystyrene |
| JP2016222837A (en) * | 2015-06-02 | 2016-12-28 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0354034A2 (en) * | 1988-08-03 | 1990-02-07 | Toray Industries, Inc. | Resin composition |
| CN105694331A (en) * | 2013-07-30 | 2016-06-22 | 江苏理工学院 | Method for preparing halogen-free flame-retardant high-impact polystyrene |
| JP2016222837A (en) * | 2015-06-02 | 2016-12-28 | 日立化成株式会社 | Thermosetting resin composition, prepreg, laminate and printed wiring board |
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| Title |
|---|
| Organophosphorus Chemistry. Ester-Chloride Conversion Under Mild Conditions at Phosphorus;Lourdes Ylagan;《Synthetic Communications》;20061205;285-289 * |
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