CN110607026A - High-strength flame-retardant regenerated plastic particles - Google Patents
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Abstract
The invention discloses a high-strength flame-retardant recycled plastic particle which is characterized by being prepared from the following raw materials in parts by weight: 60-75 parts of waste polyolefin plastic, 10-15 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 3-6 parts of 1-allyl-3-vinyl imidazole chloride salt, 3-6 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 2-5 parts of polyamide fiber, 4-8 parts of glass fiber, 3-8 parts of vinyl polyurethane, 0.5-2 parts of 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 1-3 parts of coupling agent, 0.5-1.5 parts of initiator, 0.5-1.5 parts of brightener, 0.5-1 part of plasticizer and 0.5-2 parts of antioxidant. The invention also discloses a preparation method of the high-strength flame-retardant regenerated plastic particle. The high-strength flame-retardant recycled plastic disclosed by the invention has the advantages of high strength, obvious flame-retardant effect, good toughness, excellent aging resistance and high and low temperature resistance, good performance stability and long service life.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to high-strength flame-retardant regenerated plastic particles.
Background
In recent years, with the progress of polymer material synthesis technology, the plastic industry has been rapidly advanced, and the application of plastic products has been deepened into every corner of society, and from industrial production to clothes and eating, plastic products are ubiquitous, so that plastics have become a part of people's life, and are closely related to people's life. However, while the plastic industry meets the development of people's life and society, plastic garbage brought by a large amount of waste plastics has also been secretly brought to people, which seriously affects the health and living environment of people, for example, the agricultural land begins to reduce the yield due to the influence of waste mulching films, the white pollution caused by the waste plastics begins to cause people to have headache, the non-rotten and non-decomposed lunch boxes cannot be effectively recycled, and the plastic garbage for daily use cannot be treated from the beginning.
How to solve the problem of white pollution caused by a large amount of waste plastic products is a difficult problem which is difficult and faced in the whole society at present. The preparation of the recycled plastic is an effective way for solving the pollution caused by the plastic, can effectively change waste into valuable, realizes the recycling of waste resources, and has higher economic value, social value and ecological value. However, the recycled plastic in the prior art has the defects of low strength, no toughness, low glossiness, poor thermal-oxidative stability and the like, and is easily aged and degraded under the action of heat, light, oxygen and the like in the processes of storage, processing and daily use, so that the service life of a product is seriously influenced, and the recycling range and the field of the product are limited to a certain extent. In addition, even if the impurity degree of the current advanced sorting method exceeds 5%, the existence of the impurities affects the compatibility when recycling the plastics, and the mechanical property of the recycled plastics is reduced.
Flame retardancy is another important index for evaluating the properties of recycled plastics, because only recycled plastics excellent in flame retardancy can be applied to fire-resistant materials. The traditional recycled plastics improve the flame retardant property by adding a flame retardant. The general plastic flame retardant is mainly divided into two categories of inorganic hydroxide and organic halogenated hydrocarbon, however, the inorganic hydroxide flame retardant has large dosage and damages the mechanical property of the general plastic material; the addition amount of the organic halogenated hydrocarbon flame retardant is small, but toxic volatile gas is generated after combustion, thereby polluting the environment.
Therefore, it is very important to develop a recycled plastic with excellent comprehensive performance, obvious flame retardant effect and high strength.
Disclosure of Invention
The invention mainly aims to provide the high-strength flame-retardant regenerated plastic particles, the preparation method of the regenerated plastic particles is simple and easy, the reaction conditions are mild, the large-scale production can be realized, the energy consumption in the preparation process is low, the efficiency is good, the qualification rate of finished products is high, the preparation process is green and environment-friendly, the economic value, the social value, the ecological value and the popularization and application value are higher, the waste can be efficiently, quickly and safely changed into valuable, the recycling of waste resources is realized, and the secondary pollution is low; the prepared high-strength flame-retardant regenerated plastic particles are high in strength, remarkable in flame-retardant effect, good in toughness, excellent in aging resistance and high and low temperature resistance, good in performance stability and long in service life.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: the high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 60-75 parts of waste polyolefin plastic, 10-15 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 3-6 parts of 1-allyl-3-vinyl imidazole chloride salt, 3-6 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 2-5 parts of polyamide fiber, 4-8 parts of glass fiber, 3-8 parts of vinyl polyurethane, 0.5-2 parts of 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 1-3 parts of coupling agent, 0.5-1.5 parts of initiator, 0.5-1.5 parts of brightener, 0.5-1 part of plasticizer and 0.5-2 parts of antioxidant.
Further, the waste polyolefin plastic is one of waste polypropylene plastic and waste polyethylene plastic.
Further, the antioxidant is at least one of hydroquinone, diphenylamine, naphthylamine, p-phenylenediamine and thiobisphenol.
Further, the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate and diisodecyl phthalate.
Preferably, the brightener is polyethylene glycol.
Preferably, the coupling agent is at least one selected from a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Further, the preparation method of the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate comprises the following steps: dissolving 4,4 '-diaminooctafluorobiphenyl and 4,4' -diphenylethylene dicarboxylic acid in high boiling point solvent to form solution, then adding a catalyst and a polymerization inhibitor, stirring for 10-20 minutes to obtain a mixture, transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting at the temperature of 110-120 ℃ under normal pressure for 2-4 hours, then decompressing to 50-150Pa, heating to the temperature of 260-280 ℃, preserving heat and maintaining pressure to stir and react for 15-24 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in 3-6% sodium hydroxide water solution, washing the product with ethanol for 3-5 times, and finally removing the ethanol by rotary evaporation to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate.
Preferably, the mass ratio of the 4,4 '-diaminooctafluorobiphenyl to the 4,4' -diphenylethylene dicarboxylic acid to the high boiling point solvent to the catalyst to the polymerization inhibitor is 1.22:1 (5-10): 0.3-0.5: 0.1-0.2.
Preferably, the high boiling point solvent is selected from one or more of N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide; preferably, the catalyst is at least one of ferric chloride hexahydrate, stannic chloride and lanthanum chloride; the polymerization inhibitor is at least one of tetrachlorobenzoquinone and l, 4-naphthoquinone.
Further, the preparation method of the high-strength flame-retardant recycled plastic particle comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
s2, feeding the waste polyolefin plastic raw material prepared in the S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fiber, glass fiber, vinyl polyurethane, coupling agent, initiator, brightener, plasticizer and antioxidant into a box body of a horizontal hot air circulation granulator, heating by hot air circulation at 185-200 ℃ and accelerating melting under the action of a stirring shaft at the rotation speed of 600-900 revolutions per minute to obtain a mixed melt;
and S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotation speed of 500-700 rpm for 8-18 minutes, and cooling and pelletizing the mixed material to obtain the high-strength flame-retardant regenerated plastic particles.
Preferably, the mixing temperature of the double-screw extruder is 190-235 ℃.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the high-strength flame-retardant regenerated plastic particle provided by the invention has the advantages of simple and easy preparation method, mild reaction conditions, capability of large-scale production, low energy consumption in the preparation process, good efficiency, high qualification rate of finished products, green and environment-friendly preparation process, higher economic value, social value, ecological value and popularization and application value, capability of efficiently, quickly and safely changing waste into valuables, realization of recycling of waste resources and low secondary pollution.
(2) The high-strength flame-retardant recycled plastic particle provided by the invention overcomes the defects of low strength, no toughness, low glossiness, poor thermal-oxygen stability and the like of recycled plastics in the prior art, and can be easily aged and degraded under the action of heat, light, oxygen and the like in the processes of storage, processing and daily use, so that the service life of a product is seriously influenced, and the range and the field of recycling of the product are limited to a certain extent. In addition, even if the impurity degree of the current advanced sorting method exceeds 5%, the existence of impurities affects the compatibility when the plastic is recycled, the mechanical property of the recycled plastic can be reduced, and secondly, the defect that the flame retardance needs to be further improved exists universally.
(3) In the forming stage, the waste polyolefin plastic and 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate and vinyl polyurethane are subjected to a grafting reaction to form a three-dimensional network crosslinking structure, so that the obtained regenerated plastic particles are higher in strength and more excellent in comprehensive performance, and the introduction of the polyurethane structure can endow the materials with better toughness; 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate is introduced into a fluorobiphenyl structure, so that the weather resistance, the aging resistance and the flame retardance of the regenerated plastic particles are improved; the monomer bis [2- (acryloyloxy) ethyl ] phosphate and 1, N6-vinylidene adenosine-5' -monophosphate disodium salt have a structural synergistic effect, so that the flame retardance of the regenerated plastic particles is further improved, and the components are connected in a chemical bond mode, so that the performance stability is improved.
(4) According to the high-strength flame-retardant regenerated plastic particle, the polyamide fiber and the glass fiber are introduced, the advantages of the organic fiber and the inorganic fiber are combined, the compatibility of the doped material is good, and the strength enhancement effect is good; the 1-allyl-3-vinyl imidazole chloride salt and the 1, N6-vinylidene adenosine-5' -monophosphate disodium salt are easy to generate ion exchange, the stability of the regenerated plastic particles is further improved, and the comprehensive performance of the regenerated plastic particles is improved.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. Preparation of vinyl polyurethane in the examples of the present invention reference is made to: xu Mei Heng, He you Jun, research on mechanical properties of vinyl polyurethane, thermosetting plastics, 1992(4): 26-30.
Example 1
The high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 60 parts of waste polypropylene plastic, 10 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 3 parts of 1-allyl-3-vinyl imidazole chloride salt, 3 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 2 parts of polyamide fiber, 4 parts of glass fiber, 3 parts of vinyl polyurethane, 0.5 part of 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 1 part of silane coupling agent KH 5501 part, 0.5 part of azobisisobutyronitrile, 0.5 part of polyethylene glycol, 0.5 part of dioctyl phthalate and 0.5 part of hydroquinone.
The preparation method of the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate comprises the following steps: dissolving 1.22kg of 4,4 '-diaminooctafluorobiphenyl and 1kg of 4,4' -stilbene dicarboxylic acid in 5kg of N, N-dimethylformamide to form a solution, adding 0.3kg of ferric chloride hexahydrate and 0.1kg of tetrachlorobenzoquinone, stirring for 10 minutes to obtain a mixture, then transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting for 2 hours at 110 ℃ under normal pressure, then reducing the pressure to 50Pa, heating to 260 ℃, keeping the temperature and pressure to perform stirring and reacting for 15 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in a 3% sodium hydroxide aqueous solution, washing the product with ethanol for 3 times, and finally performing rotary evaporation to remove the ethanol to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate.
The preparation method of the high-strength flame-retardant recycled plastic particles comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
step S2, feeding the waste polyolefin plastic raw material prepared in the step S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fibers, glass fibers, vinyl polyurethane, a silane coupling agent KH550, azobisisobutyronitrile, polyethylene glycol, dioctyl phthalate and hydroquinone into a box body in a horizontal hot air circulation granulator, heating the mixture by hot air circulation at 185 ℃, and accelerating the mixture to melt under the action of a stirring shaft at the rotating speed of 600 revolutions per minute to obtain a mixed melt;
step S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotating speed of 500 revolutions per minute for 8 minutes, and cooling and pelletizing the mixed material to obtain high-strength flame-retardant regenerated plastic particles; the mixing temperature of the double-screw extruder is 190 ℃.
Example 2
The high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 64 parts of waste polyethylene plastic, 11 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 4 parts of 1-allyl-3-vinyl imidazole chloride salt, 4 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 3 parts of polyamide fiber, 5 parts of glass fiber, 4 parts of vinyl polyurethane, 0.8 part of 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 0.8 part of silane coupling agent KH5601.5 part, 0.8 part of azo-diisoheptanonitrile, 0.8 part of polyethylene glycol, 0.6 part of dibutyl phthalate and 0.7 part of diphenylamine.
The preparation method of the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate comprises the following steps: dissolving 1.22kg of 4,4 '-diaminooctafluorobiphenyl and 1kg of 4,4' -diphenylethylene dicarboxylic acid in 6kg of N-methylpyrrolidone to form a solution, adding 0.35kg of tin chloride and 0.12kg of l, 4-naphthoquinone, stirring for 12 minutes to obtain a mixture, transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting for 2.5 hours at the temperature of 113 ℃ under normal pressure, then reducing the pressure to 70Pa, heating to 265 ℃, keeping the temperature and pressure to perform stirring and reacting for 17 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in a sodium hydroxide aqueous solution with the mass fraction of 4%, washing the product with ethanol for 3-5 times, and finally performing rotary evaporation to remove the ethanol to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate.
The preparation method of the high-strength flame-retardant recycled plastic particles comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
step S2, feeding the waste polyolefin plastic raw material prepared in the step S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fibers, glass fibers, vinyl polyurethane, a silane coupling agent KH560, azobisisoheptonitrile, polyethylene glycol, dibutyl phthalate and diphenylamine into a box body in a horizontal hot air circulation granulator, heating the mixture by hot air circulation at 190 ℃, and accelerating the mixture to melt under the action of a stirring shaft at the rotating speed of 700 revolutions per minute to obtain a mixed melt;
step S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotation speed of 550 revolutions per minute for 10 minutes, and cooling and pelletizing the mixed material to obtain high-strength flame-retardant regenerated plastic particles; the mixing temperature of the twin-screw extruder was 215 ℃.
Example 3
The high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 67 parts of waste polypropylene plastic, 13 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 4.5 parts of 1-allyl-3-vinyl imidazole chloride salt, 4.5 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 3.5 parts of polyamide fiber, 6 parts of glass fiber, 6 parts of vinyl polyurethane, 1.4 parts of 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 1.02 parts of silane coupling agent KH 5702 parts, 1.1 parts of azobisisobutyronitrile, 1.1 parts of polyethylene glycol, 0.7 part of diisononyl phthalate and 1.3 parts of naphthylamine.
The preparation method of the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate comprises the following steps: dissolving 1.22kg of 4,4 '-diaminooctafluorobiphenyl and 1kg of 4,4' -diphenylethylene dicarboxylic acid in 7kg of N, N-dimethylacetamide to form a solution, adding 0.4kg of lanthanum chloride and 0.15kg of tetrachlorobenzoquinone, stirring for 15 minutes to obtain a mixture, transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting for 3 hours at 115 ℃ under normal pressure, then reducing the pressure to 80Pa, heating to 270 ℃, keeping the temperature and pressure for stirring and reacting for 20 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in a sodium hydroxide aqueous solution with the mass fraction of 4.5%, washing the product with ethanol for 4 times, and finally removing the ethanol by rotary evaporation to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate.
The preparation method of the high-strength flame-retardant recycled plastic particles comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
step S2, feeding the waste polyolefin plastic raw material prepared in the step S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fibers, glass fibers, vinyl polyurethane, a silane coupling agent KH570, azobisisobutyronitrile, polyethylene glycol, diisononyl phthalate and naphthylamine into a box body in a horizontal hot air circulation granulator, heating the mixture by hot air circulation at the temperature of 192 ℃, and accelerating the melting under the action of a stirring shaft at the rotating speed of 750 revolutions per minute to obtain a mixed melt;
step S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotating speed of 600 revolutions per minute for 13 minutes, and cooling and pelletizing the mixed material to obtain high-strength flame-retardant regenerated plastic particles; the mixing temperature of the twin-screw extruder is 220 ℃.
Example 4
The high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 73 parts of waste polyethylene plastic, 14 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 5 parts of 1-allyl-3-vinyl imidazole chloride salt, 5 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 4.5 parts of polyamide fiber, 7 parts of glass fiber, 7 parts of vinyl polyurethane, 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 2.5 parts of coupling agent, 1.4 parts of initiator, 1.4 parts of brightening agent, 0.9 part of plasticizer and 1.9 parts of antioxidant.
The antioxidant is prepared by mixing hydroquinone, diphenylamine, naphthylamine, p-phenylenediamine and thiobisphenol in a mass ratio of 1:1:3:2: 2; the plasticizer is prepared by mixing dioctyl phthalate, dibutyl phthalate, diisononyl phthalate and diisodecyl phthalate according to the mass ratio of 1:3:5: 2; the brightener is polyethylene glycol; the coupling agent is prepared by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:3: 2; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5.
The preparation method of the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate comprises the following steps: dissolving 1.22kg of 4,4 '-diaminooctafluorobiphenyl and 1kg of 4,4' -diphenylethylene dicarboxylic acid in 9kg of high-boiling-point solvent to form a solution, adding 0.45kg of catalyst and 0.19kg of polymerization inhibitor, stirring for 19 minutes to obtain a mixture, transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting for 3.8 hours at the temperature of 119 ℃ under normal pressure, then decompressing to 140Pa, heating to 278 ℃, keeping the temperature and pressure to perform stirring and reacting for 23 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in a sodium hydroxide aqueous solution with the mass fraction of 5%, washing the product with ethanol for 5 times, and finally performing rotary evaporation to remove the ethanol to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate.
The high-boiling-point solvent is formed by mixing N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide according to a mass ratio of 1:3: 2; the catalyst is prepared by mixing ferric chloride hexahydrate, stannic chloride and lanthanum chloride according to the mass ratio of 1:2: 5; the polymerization inhibitor is formed by mixing tetrachlorobenzoquinone and l, 4-naphthoquinone according to a mass ratio of 3: 5.
The preparation method of the high-strength flame-retardant recycled plastic particles comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
step S2, feeding the waste polyolefin plastic raw material prepared in the step S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fiber, glass fiber, vinyl polyurethane, coupling agent, initiator, brightener, plasticizer and antioxidant into a box body of a horizontal hot air circulation granulator, heating by hot air circulation at 198 ℃, and accelerating melting under the action of a stirring shaft at the rotation speed of 850 revolutions per minute to obtain a mixed melt;
step S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotating speed of 680 r/min for 16 min, and cooling and pelletizing the mixed material to obtain high-strength flame-retardant regenerated plastic particles; the mixing temperature of the twin-screw extruder is 230 ℃.
Example 5
The high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 75 parts of waste polypropylene plastic, 15 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 6 parts of 1-allyl-3-vinyl imidazole chloride salt, 6 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 5 parts of polyamide fiber, 8 parts of glass fiber, 8 parts of vinyl polyurethane, 2 parts of 1, N6-vinylidene adenosine-5 ' -monosodium monophosphate, 3 parts of silane coupling agent KH 5503 parts, 1.5 parts of azobisisoheptonitrile, 1.5 parts of polyethylene glycol, 1 part of diisodecyl phthalate and 2 parts of thiobisphenol.
The preparation method of the 4,4 '-diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate comprises the following steps: dissolving 1.22kg of 4,4 '-diaminooctafluorobiphenyl and 1kg of 4,4' -diphenylethylene dicarboxylic acid in 10kg of N-methylpyrrolidone to form a solution, adding 0.5kg of tin chloride and 0.2kg of tetrachlorobenzoquinone, stirring for 20 minutes to obtain a mixture, transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting for 4 hours at 120 ℃ under normal pressure, then decompressing to 150Pa, heating to 280 ℃, keeping the temperature and pressure for stirring and reacting for 24 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in a sodium hydroxide aqueous solution with the mass fraction of 6%, washing the product with ethanol for 5 times, and finally removing the ethanol by rotary evaporation to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate.
The preparation method of the high-strength flame-retardant recycled plastic particles comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
step S2, feeding the waste polyolefin plastic raw material prepared in the step S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fiber, glass fiber, vinyl polyurethane, coupling agent, initiator, brightener, plasticizer and antioxidant into a box body of a horizontal hot air circulation granulator, heating by hot air circulation at the heating temperature of 200 ℃, and accelerating melting under the action of a stirring shaft at the rotation speed of 900 revolutions per minute to obtain a mixed melt;
step S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotating speed of 700 revolutions per minute for 18 minutes, and cooling and pelletizing the mixed material to obtain high-strength flame-retardant regenerated plastic particles; the mixing temperature of the double-screw extruder is 235 ℃.
Comparative example 1
This example provides a high-strength flame-retardant recycled plastic pellet, substantially the same as in example 1, except that the polycondensate of 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide was not added.
Comparative example 2
This example provides a high strength flame retardant recycled plastic pellet, essentially the same as example 1, except that no 1-allyl-3-vinylimidazole chloride salt was added.
Comparative example 3
This example provides a high strength flame retardant recycled plastic pellet substantially the same as example 1 except that bis [2- (acryloyloxy) ethyl ] phosphate was not added.
Comparative example 4
This example provides a high strength flame retardant recycled plastic pellet, essentially the same as example 1, except that 1, N6-vinylidene adenosine-5' -monophosphate disodium salt was not added.
Comparative example 5
This example provides a high strength flame retardant recycled plastic pellet, essentially the same as example 1, except that no vinyl polyurethane was added.
Comparative example 6
The present example provides an environment-friendly recycled plastic pellet, the formulation and preparation method of which are the same as those of the embodiment 1 of the Chinese patent application publication No. CN 108659380A.
To further illustrate the beneficial technical effects of the recycled plastic particles involved in the examples of the present invention, the recycled plastic particles described in examples 1-5 and comparative examples 1-6 above were subjected to performance tests, and the test results and test methods are shown in Table 1.
TABLE 1
| Item | Tensile strength | Impact resistance | Limiting oxygen index | Vicat softening point |
| Unit of | MPa | J/M | ％ | ℃ |
| Test standard | GB/T1040-2006 | ASTMD256 | GB5454-85 | GB 1633-1979 |
| Example 1 | 54.0 | 330 | 38.0 | 120 |
| Example 2 | 54.2 | 332 | 38.3 | 123 |
| Example 3 | 54.3 | 335 | 38.7 | 125 |
| Example 4 | 54.5 | 338 | 39.2 | 128 |
| Example 5 | 55.0 | 340 | 40.1 | 131 |
| Comparative example 1 | 44.5 | 313 | 28.4 | 108 |
| Comparative example 2 | 43.8 | 315 | 28.0 | 105 |
| Comparative example 3 | 44.4 | 310 | 26.7 | 110 |
| Comparative example 4 | 45.1 | 309 | 29.0 | 107 |
| Comparative example 5 | 43.3 | 313 | 28.9 | 105 |
| Comparative example 6 | 43.1 | 300 | 22.6 | 102 |
As can be seen from Table 1, the high-strength flame-retardant recycled plastic particles disclosed by the embodiment of the invention have tensile strength of more than or equal to 54.0MPa, impact resistance of more than or equal to 330J/M, limiting oxygen index of more than or equal to 38.0 percent and Vicat softening point of more than or equal to 120 ℃; the tensile strength of the recycled plastic particles in the comparative example is less than or equal to 45.1MPa, the impact resistance is less than or equal to 315J/M, the limiting oxygen index is less than or equal to 29.0 percent, and the Vicat softening point is less than or equal to 110 ℃. Therefore, the addition of the 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, the 1-allyl-3-vinyl imidazole chloride salt, the bis [2- (acryloyloxy) ethyl ] phosphate, the vinyl polyurethane and the 1, N6-vinylidene adenosine-5 ' -monosodium monophosphate has an improvement effect on the mechanical property, the high temperature resistance and the flame retardance of the material.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The high-strength flame-retardant regenerated plastic particle is characterized by being prepared from the following raw materials in parts by weight: 60-75 parts of waste polyolefin plastic, 10-15 parts of 4,4' -diaminooctafluorobiphenyl/4, 4' -stilbene dicarboxylic acid polyamide polycondensate, 3-6 parts of 1-allyl-3-vinyl imidazole chloride salt, 3-6 parts of bis [2- (acryloyloxy) ethyl ] phosphate, 2-5 parts of polyamide fiber, 4-8 parts of glass fiber, 3-8 parts of vinyl polyurethane, 0.5-2 parts of 1, N6-vinylidene adenosine-5 ' -monophosphate disodium salt, 1-3 parts of coupling agent, 0.5-1.5 parts of initiator, 0.5-1.5 parts of brightener, 0.5-1 part of plasticizer and 0.5-2 parts of antioxidant.
2. The high-strength flame-retardant recycled plastic granules as claimed in claim 1, wherein the waste polyolefin plastic is one of waste polypropylene plastic and waste polyethylene plastic.
3. The high strength flame retardant recycled plastic granules of claim 1, wherein said antioxidant is at least one of hydroquinone, diphenylamine, naphthylamine, p-phenylenediamine, thiobisphenol.
4. The high-strength flame-retardant recycled plastic granules according to claim 1, wherein the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, diisodecyl phthalate; the brightener is polyethylene glycol; the coupling agent is at least one selected from a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570; the initiator is at least one of azodiisobutyronitrile and azodiisoheptonitrile.
5. The high-strength flame-retardant recycled plastic granules according to claim 1, wherein said 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate is prepared by a method comprising the steps of: dissolving 4,4 '-diaminooctafluorobiphenyl and 4,4' -diphenylethylene dicarboxylic acid in high boiling point solvent to form solution, then adding a catalyst and a polymerization inhibitor, stirring for 10-20 minutes to obtain a mixture, transferring the mixture into a reaction kettle which is subjected to nitrogen pressure maintaining treatment, stirring and reacting at the temperature of 110-120 ℃ under normal pressure for 2-4 hours, then decompressing to 50-150Pa, heating to the temperature of 260-280 ℃, preserving heat and maintaining pressure to stir and react for 15-24 hours, naturally cooling to room temperature after the reaction is finished, then precipitating in 3-6% sodium hydroxide water solution, washing the product with ethanol for 3-5 times, and finally removing the ethanol by rotary evaporation to obtain the 4,4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate.
6. The high-strength flame-retardant recycled plastic granules as claimed in claim 5, wherein the mass ratio of 4,4 '-diaminooctafluorobiphenyl to 4,4' -diphenylethylene dicarboxylic acid to high-boiling solvent to catalyst to polymerization inhibitor is 1.22:1 (5-10) to (0.3-0.5) to (0.1-0.2).
7. The high-strength flame-retardant recycled plastic granules according to claim 5, wherein the high-boiling-point solvent is one or more selected from N, N-dimethylformamide, N-methylpyrrolidone and N, N-dimethylacetamide.
8. The high-strength flame-retardant recycled plastic granules according to claim 5, wherein the catalyst is at least one of ferric chloride hexahydrate, tin chloride and lanthanum chloride; the polymerization inhibitor is at least one of tetrachlorobenzoquinone and l, 4-naphthoquinone.
9. The high-strength flame-retardant recycled plastic particle as claimed in any one of claims 1 to 8, wherein the preparation method of the high-strength flame-retardant recycled plastic particle comprises the following steps:
s1, sequentially crushing, cleaning, dehydrating and drying the screened waste polyolefin plastics to obtain waste polyolefin plastic raw materials;
s2, feeding the waste polyolefin plastic raw material prepared in the S1, 4 '-diaminooctafluorobiphenyl/4, 4' -diphenylethylene dicarboxylic acid polyamide polycondensate, 1-allyl-3-vinyl imidazole chloride salt, bis [2- (acryloyloxy) ethyl ] phosphate, polyamide fiber, glass fiber, vinyl polyurethane, coupling agent, initiator, brightener, plasticizer and antioxidant into a box body of a horizontal hot air circulation granulator, heating by hot air circulation at 185-200 ℃ and accelerating melting under the action of a stirring shaft at the rotation speed of 600-900 revolutions per minute to obtain a mixed melt;
and S3, mixing the mixed melt prepared in the step S2 in a double-screw extruder at the rotation speed of 500-700 rpm for 8-18 minutes, and cooling and pelletizing the mixed material to obtain the high-strength flame-retardant regenerated plastic particles.
10. The recycled plastic granules with high strength and flame retardancy as claimed in claim 9, wherein the mixing temperature of the twin-screw extruder is 190 ℃ and 235 ℃.
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| CN113604035A (en) * | 2021-08-20 | 2021-11-05 | 安徽瑞琦塑胶科技有限公司 | Flame-retardant wear-resistant plastic particle and processing technology thereof |
| CN113604035B (en) * | 2021-08-20 | 2023-04-18 | 安徽瑞琦塑胶科技有限公司 | Flame-retardant wear-resistant plastic particle and processing technology thereof |
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