CN112080117B - Environment-friendly high-heat-resistance flame-retardant modified plastic and processing technology thereof - Google Patents
Environment-friendly high-heat-resistance flame-retardant modified plastic and processing technology thereof Download PDFInfo
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- CN112080117B CN112080117B CN202011042873.0A CN202011042873A CN112080117B CN 112080117 B CN112080117 B CN 112080117B CN 202011042873 A CN202011042873 A CN 202011042873A CN 112080117 B CN112080117 B CN 112080117B
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Abstract
The invention discloses an environment-friendly high heat-resistant flame-retardant modified plastic and a processing technology thereof, wherein starch and modified polylactic acid are used as a plastic main body, epoxy resin is added into the modified plastic, epoxy groups carried on the epoxy resin can react with hydroxyl groups on the starch and hydroxyl groups on the polylactic acid and carboxyl groups on the polylactic acid under the action of high temperature and high shearing force, so that the combination effect of the starch and the polylactic acid in a mixed system is improved, the strength of a formed plastic product is improved, wherein nano organic montmorillonite is fixed on the surface of modified glass fiber through the epoxy resin, the dispersion effect of the glass fiber in the mixed system and the combination effect of the glass fiber and the starch and the polylactic acid in a dispersion system can be improved by the epoxy resin fixed on the surface of the modified glass fiber, the strength of the plastic is improved, and meanwhile, the nano organic montmorillonite fixed on the surface of the glass fiber has the flame-retardant or flame-retardant property of the plastic product can be improved.
Description
Technical Field
The invention belongs to the technical field of environment-friendly high polymer materials, and particularly relates to environment-friendly high heat-resistant flame-retardant modified plastic and a processing technology thereof.
Background
The main component of the plastic is resin. The resin is a polymer compound which has not been mixed with various additives. The term resin is originally named by lipids secreted from animals and plants, such as rosin, shellac, etc. The resin accounts for 40-100% of the total weight of the plastic. The basic properties of plastics are mainly determined by the nature of the resin, but additives also play an important role. Some plastics are composed essentially of synthetic resins, with no or little additives, such as organic glass, polystyrene, etc.
The plastic has wide application in various fields, but as the usage amount of the plastic increases year by year, the plastic pollution is seriously damaged due to the non-degradability of most plastic products, so that the plastic product with the degradability is one of the problems to be solved in the prior art, and the polylactic acid is a degradable plastic product and is a degradable plastic material commonly used in the prior art, but the application range of the polylactic acid degradable plastic is directly reduced due to the lower softening point of the polylactic acid, and the polylactic acid plastic has inflammable property, so that the application range of the polylactic acid plastic product is limited, and the invention provides the following technical scheme for solving the problems.
Disclosure of Invention
The invention aims to provide an environment-friendly high heat-resistant flame-retardant modified plastic and a processing technology thereof.
The technical problems to be solved by the invention are as follows:
polylactic acid is a degradable plastic product and is a degradable plastic material commonly used in the prior art, but the use range of polylactic acid degradable plastic is directly reduced due to the low softening point of polylactic acid, and polylactic acid plastic has inflammable property, so that the use range of polylactic acid plastic products is limited.
The aim of the invention can be achieved by the following technical scheme:
an environment-friendly high heat-resistant flame-retardant modified plastic is prepared from the following raw materials: modified polylactic acid, modified starch, epoxy resin and modified glass fiber, wherein the weight ratio of the raw materials is that the modified polylactic acid: modified starch: epoxy resin: modified glass fiber = 100:10-55:3-7:1-3;
the processing technology of the environment-friendly high heat-resistant flame-retardant modified plastic comprises the following steps:
firstly, preparing modified glass fibers;
adding starch into deionized water, stirring and dispersing to obtain starch dispersion, heating to 80-90 ℃ to gelatinize the starch, cooling the obtained gelatinized starch to 30-45 ℃, adding an initiator into the gelatinized starch, stirring and uniformly mixing, adding a grafting monomer into the gelatinized starch, regulating the reaction temperature to 40-50 ℃, stirring and reacting at constant temperature for 2-3 hours, and dehydrating and crushing to obtain modified starch;
wherein the initiator is cerium ammonium nitrate, and the addition amount of the initiator is 2-4.5% of the weight of the starch;
the grafting monomer is a uniform mixture of methyl methacrylate and vinyl acetate according to a weight ratio of 1-2.4:1, and the addition amount of the grafting monomer is 9% -13.5% of the weight of the starch;
and thirdly, uniformly mixing the modified polylactic acid, the modified starch, the epoxy resin and the modified glass fiber according to the weight ratio, and extruding the mixture through a double-screw extruder to obtain the environment-friendly high-heat-resistance flame-retardant modified plastic.
Wherein the double screw extrusion temperature is 150-170 ℃ and the screw rotation speed is 100r/min;
the method is characterized in that starch and modified polylactic acid are used as a plastic main body, epoxy resin is added into the plastic main body, epoxy groups carried on the epoxy resin can react with hydroxyl groups on the starch and hydroxyl groups and carboxyl groups on the polylactic acid under the action of high temperature and high shearing force, so that the combination effect of the starch and the polylactic acid in a mixed system is improved, the strength of a formed plastic product is improved, nano organic montmorillonite is fixed on the surface of modified glass fiber through the epoxy resin, the dispersion effect of the glass fiber in the mixed system and the combination effect of the glass fiber and the starch and the polylactic acid in the dispersion system can be improved, the strength of the plastic is improved, and meanwhile, the glass fiber and the nano organic montmorillonite fixed on the surface of the glass fiber have the flame retardant or incombustible characteristics, and the flame retardant capability of the plastic product can be improved;
the preparation method of the modified polylactic acid comprises the following steps:
SS1, preparing an acetic acid aqueous solution with the pH value of 4.5-6, adding hexadecyl trimethyl ammonium bromide into the aqueous solution, uniformly mixing and stirring, adding montmorillonite into the aqueous solution, stirring and dispersing, performing ultrasonic dispersion for 10-13min at the frequency of 60-160KHz, adjusting the reaction temperature to 75-85 ℃, performing heat preservation reaction for 2.5-3h, filtering, and drying the montmorillonite at the temperature of 65-80 ℃ to obtain organic modified montmorillonite;
SS2, uniformly mixing the organic modified montmorillonite obtained in the step SS1 with polylactic acid according to the weight ratio of 1:9-14, and extruding and granulating by a double-screw extruder to obtain modified polylactic acid, wherein the double-screw extrusion temperature is 150-170 ℃ and the screw rotation speed is 120r/min;
according to the invention, the surface organic modified montmorillonite is blended in the polylactic acid, so that the crystallization speed of the polylactic acid is improved, the thermal deformation temperature of the polylactic acid is improved, the montmorillonite has a good flame retardant effect, and the flame retardant and flame-inhibiting function of the material is improved.
The preparation method of the modified glass fiber comprises the following steps:
s1, adding nano organic montmorillonite into deionized water, wherein the weight ratio of the nano organic montmorillonite to the deionized water is 1:5-9, stirring and dispersing uniformly, freeze-drying the dispersion liquid, then adding the dispersion liquid into a ball mill, firstly dry-grinding for 5-9min under the condition of the rotating speed of 240-380r/min to crush massive organic montmorillonite, then adding the deionized water into the dispersion liquid, and continuing ball milling for 20-35min at the rotating speed to obtain montmorillonite slurry, and adding the deionized water into the montmorillonite slurry to obtain nano organic montmorillonite dispersion liquid, wherein the mass percentage of the nano organic montmorillonite is 20% -35%;
s2, preparing a water-based epoxy resin emulsion with the solid content of 18-25%, adding the water-based epoxy resin emulsion into the nano organic montmorillonite dispersion liquid in the stirring process, and after the water-based epoxy resin emulsion is completely added, increasing the stirring speed to 1600-2200r/min and stirring for 10-18min to obtain a coating liquid;
s3, adding the glass fiber into a sodium hydroxide solution with the pH of 10.5-12.5, stirring and soaking for 3-8min, then flushing with a mixed solution of deionized water and ethanol to be neutral, and then drying at the temperature of 60-90 ℃ for later use;
the mixed solution of deionized water and ethanol refers to a uniform mixture of deionized water and ethanol according to a volume ratio of 1:0.3-3;
s4, adding the glass fiber treated in the step S3 into the coating liquid prepared in the step S2, carrying out ultrasonic treatment at the frequency of 60-100KHz for 5-10min, standing for 15-30min, taking out the glass fiber, and drying at the temperature of 65-70 ℃ after draining to obtain a glass fiber intermediate;
s5, adding the glass fiber intermediate obtained in the step S4 into a sodium hydroxide solution with the pH value of 10-11.5, soaking for 4-7min, taking out the glass fiber intermediate, washing with deionized water to be neutral, and drying at the temperature of 60-90 ℃ to obtain the modified glass fiber.
In the step, firstly, a coating liquid with a composite structure of nano organic montmorillonite and water-based epoxy resin emulsion is prepared by mixing the nano organic montmorillonite dispersion liquid with the water-based epoxy resin emulsion at a high speed, then the surface of glass fiber is treated by dilute alkali solution, the roughness of the surface of the glass fiber is improved, the adsorption capacity of the surface of the glass fiber is improved, then the treated glass fiber is added into the coating liquid, the ultrasonic treatment is carried out, the surface of the glass fiber is adsorbed with the water-based epoxy resin emulsion, the water-based epoxy resin emulsion is used for fixing the nano organic montmorillonite on the surface of the glass fiber after drying, then the treated glass is added into sodium hydroxide solution again for soaking treatment, and the exposed part of the glass fiber is continuously treated, so that the roughness of the surface of the glass fiber is further improved.
The invention has the beneficial effects that:
the environment-friendly high heat-resistant flame-retardant modified plastic disclosed by the invention is characterized in that starch and modified polylactic acid are used as a plastic main body, epoxy resin is added into the plastic main body, epoxy groups carried on the epoxy resin can react with hydroxyl groups on the starch and hydroxyl groups and carboxyl groups on the polylactic acid under the action of high temperature and high shearing force, so that the combination effect of the starch and the polylactic acid in a mixed system is improved, the strength of a formed plastic product is improved, nano organic montmorillonite is fixed on the surface of modified glass fiber through the epoxy resin, the dispersion effect of glass fiber in the mixed system and the combination effect of the glass fiber and the starch and the polylactic acid in the dispersion system can be improved, the strength of the plastic is improved, and meanwhile, the glass fiber and the nano organic montmorillonite fixed on the surface of the glass fiber have the flame-retardant or flame-retardant property of the plastic product can be improved; according to the modified polylactic acid disclosed by the invention, the montmorillonite with the surface being organically modified is blended in the polylactic acid, so that the crystallization speed of the polylactic acid is improved, the thermal deformation temperature of the polylactic acid is improved, the montmorillonite has a good flame retardant effect, and the flame retardant and flame-inhibiting function of the material is improved. According to the preparation method of the modified glass fiber, firstly, a nano organic montmorillonite dispersion liquid and a water-based epoxy resin emulsion are mixed at a high speed, so that a coating liquid with a composite structure is prepared, wherein the surface of the coating liquid is coated with the water-based epoxy resin emulsion, the surface of the glass fiber is treated by dilute alkali solution, the roughness of the surface of the glass fiber is improved, the adsorption capacity of the surface of the glass fiber is improved, the treated glass fiber is added into the coating liquid, the coating liquid is subjected to standing treatment after ultrasonic treatment, the surface of the glass fiber is adsorbed with the water-based epoxy resin emulsion, the water-based epoxy resin emulsion is used for fixing the nano organic montmorillonite on the surface of the glass fiber after drying and drying, then the treated glass is added into a sodium hydroxide solution again for soaking treatment, and the exposed part of the glass fiber is continuously treated, so that the roughness of the surface of the glass fiber is further improved, and the connection strength of the glass fiber in a plastic mixed system is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An environment-friendly high heat-resistant flame-retardant modified plastic is prepared from the following raw materials: modified polylactic acid, modified starch, epoxy resin and modified glass fiber, wherein the weight ratio of the raw materials is that the modified polylactic acid: modified starch: epoxy resin: modified glass fiber = 100:30:5:2.5;
the processing technology of the environment-friendly high heat-resistant flame-retardant modified plastic comprises the following steps:
firstly, preparing modified glass fibers;
secondly, adding starch into deionized water, stirring and dispersing to obtain starch dispersion liquid, heating to 88 ℃ to gelatinize the starch, cooling the obtained gelatinized starch to 40 ℃, adding an initiator into the gelatinized starch, stirring and uniformly mixing, adding a grafting monomer into the gelatinized starch, regulating the reaction temperature to 45 ℃, stirring and reacting at constant temperature for 3 hours, and dehydrating and crushing to obtain modified starch;
wherein the initiator is cerium ammonium nitrate, and the addition amount of the initiator is 3.5% of the weight of the starch;
the grafting monomer is a uniform mixture of methyl methacrylate and vinyl acetate according to a weight ratio of 2.2:1, and the addition amount of the grafting monomer is 12% of the weight of starch;
and thirdly, uniformly mixing the modified polylactic acid, the modified starch, the epoxy resin and the modified glass fiber according to the weight ratio, and extruding the mixture through a double-screw extruder to obtain the environment-friendly high-heat-resistance flame-retardant modified plastic.
Wherein the double-screw extrusion temperature is 165 ℃, and the screw rotating speed is 100r/min;
the preparation method of the modified polylactic acid comprises the following steps:
SS1, preparing an acetic acid aqueous solution with pH value of 5, then adding hexadecyl trimethyl ammonium bromide into the aqueous solution, uniformly mixing and stirring, adding montmorillonite into the aqueous solution, stirring and dispersing, performing ultrasonic dispersion for 12min at a frequency of 100KHz, then adjusting the reaction temperature to 80 ℃, performing heat preservation reaction for 2.5h, filtering, and drying the montmorillonite at 75 ℃ to obtain organic modified montmorillonite;
SS2, uniformly mixing the organic modified montmorillonite obtained in the step SS1 with polylactic acid according to the weight ratio of 1:11, and extruding and granulating by a double-screw extruder to obtain modified polylactic acid, wherein the double-screw extrusion temperature is 165 ℃, and the screw rotation speed is 120r/min;
the preparation method of the modified glass fiber comprises the following steps:
s1, adding nano organic montmorillonite into deionized water, wherein the weight ratio of the nano organic montmorillonite to the deionized water is 1:7, stirring and dispersing uniformly, freeze-drying the dispersion liquid, then adding the dispersion liquid into a ball mill, dry-grinding for 7min at the rotating speed of 260r/min to crush massive organic montmorillonite, adding the deionized water into the dispersion liquid, keeping the rotating speed for ball milling for 30min to obtain montmorillonite slurry, and adding the deionized water into the montmorillonite slurry to obtain nano organic montmorillonite dispersion liquid, wherein the mass percentage of the nano organic montmorillonite is 25%;
s2, preparing a water-based epoxy resin emulsion with the solid content of 20%, adding the water-based epoxy resin emulsion into the nano organic montmorillonite dispersion liquid in the stirring process, and after the water-based epoxy resin emulsion is completely added, lifting the stirring speed to 2000r/min and stirring for 16min to obtain a coating liquid, wherein the volume ratio of the nano organic montmorillonite dispersion liquid to the water-based epoxy resin emulsion is 1:2;
s3, adding the glass fiber into a sodium hydroxide solution with the pH of 11.5, stirring and soaking for 6min, then flushing the glass fiber to be neutral by using a mixed solution of deionized water and ethanol, and then drying the glass fiber at the temperature of 75 ℃ for later use;
the mixed solution of deionized water and ethanol refers to a uniform mixture of deionized water and ethanol according to a volume ratio of 1:1;
s4, adding the glass fiber treated in the step S3 into the coating liquid prepared in the step S2, carrying out ultrasonic treatment at the frequency of 80KHz for 6min, standing for 20min, taking out the glass fiber, draining, and drying at the temperature of 70 ℃ to obtain a glass fiber intermediate;
and S5, adding the glass fiber intermediate obtained in the step S4 into a sodium hydroxide solution with the pH value of 11.5, soaking for 5min, taking out the glass fiber intermediate, washing with deionized water to be neutral, and drying at the temperature of 75 ℃ to obtain the modified glass fiber.
Example 2
An environment-friendly high heat-resistant flame-retardant modified plastic is prepared from the following raw materials: modified polylactic acid, modified starch, epoxy resin and modified glass fiber, wherein the weight ratio of the raw materials is that the modified polylactic acid: modified starch: epoxy resin: modified glass fiber = 100:20:5:3, a step of;
the processing technology of the environment-friendly high heat-resistant flame-retardant modified plastic comprises the following steps:
firstly, preparing modified glass fibers;
secondly, adding starch into deionized water, stirring and dispersing to obtain starch dispersion liquid, heating to 85 ℃ to gelatinize the starch, cooling the obtained gelatinized starch to 35 ℃, adding an initiator into the gelatinized starch, stirring and uniformly mixing, adding a grafting monomer into the gelatinized starch, regulating the reaction temperature to 45 ℃, stirring and reacting at constant temperature for 2 hours, and dehydrating and crushing to obtain modified starch;
wherein the initiator is cerium ammonium nitrate, and the addition amount of the initiator is 3.5% of the weight of the starch;
the grafting monomer is a uniform mixture of methyl methacrylate and vinyl acetate according to a weight ratio of 2:1, and the addition amount of the grafting monomer is 12% of the weight of starch;
and thirdly, uniformly mixing the modified polylactic acid, the modified starch, the epoxy resin and the modified glass fiber according to the weight ratio, and extruding the mixture through a double-screw extruder to obtain the environment-friendly high-heat-resistance flame-retardant modified plastic.
Wherein the double-screw extrusion temperature is 160 ℃, and the screw rotating speed is 100r/min;
the preparation method of the modified polylactic acid comprises the following steps:
SS1, preparing an acetic acid aqueous solution with pH value of 5, then adding hexadecyl trimethyl ammonium bromide into the aqueous solution, uniformly mixing and stirring, adding montmorillonite into the aqueous solution, stirring and dispersing, performing ultrasonic dispersion for 10min at the frequency of 120KHz, then adjusting the reaction temperature to 80 ℃, performing heat preservation reaction for 2.5h, filtering, and drying the montmorillonite at 70 ℃ to obtain organic modified montmorillonite;
SS2, uniformly mixing the organic modified montmorillonite obtained in the step SS1 with polylactic acid according to the weight ratio of 1:12, and extruding and granulating by a double-screw extruder to obtain modified polylactic acid, wherein the double-screw extrusion temperature is 160 ℃, and the screw rotation speed is 120r/min;
the preparation method of the modified glass fiber comprises the following steps:
s1, adding nano organic montmorillonite into deionized water, wherein the weight ratio of the nano organic montmorillonite to the deionized water is 1:7, stirring and dispersing uniformly, freeze-drying the dispersion liquid, then adding the dispersion liquid into a ball mill, dry-grinding for 7min at the rotating speed of 300r/min to crush massive organic montmorillonite, adding the deionized water into the dispersion liquid, keeping the rotating speed for ball milling for 30min to obtain montmorillonite slurry, and adding the deionized water into the montmorillonite slurry to obtain nano organic montmorillonite dispersion liquid, wherein the mass percentage of the nano organic montmorillonite is 25%;
s2, preparing a water-based epoxy resin emulsion with the solid content of 23%, adding the water-based epoxy resin emulsion into the nano organic montmorillonite dispersion liquid in the stirring process, and after the water-based epoxy resin emulsion is completely added, lifting the stirring speed to 2000r/min and stirring for 13min to obtain a coating liquid, wherein the volume ratio of the nano organic montmorillonite dispersion liquid to the water-based epoxy resin emulsion is 1:2.5;
s3, adding the glass fiber into a sodium hydroxide solution with the pH of 11.5, stirring and soaking for 4min, then flushing the glass fiber to be neutral by using a mixed solution of deionized water and ethanol, and then drying the glass fiber at the temperature of 80 ℃ for later use;
the mixed solution of deionized water and ethanol refers to a uniform mixture of deionized water and ethanol according to a volume ratio of 1:1;
s4, adding the glass fiber treated in the step S3 into the coating liquid prepared in the step S2, carrying out ultrasonic treatment at the frequency of 80KHz for 8min, standing for 25min, taking out the glass fiber, draining, and drying at the temperature of 70 ℃ to obtain a glass fiber intermediate;
and S5, adding the glass fiber intermediate obtained in the step S4 into a sodium hydroxide solution with the pH value of 11.5, soaking for 6min, taking out the glass fiber intermediate, washing with deionized water to be neutral, and drying at the temperature of 80 ℃ to obtain the modified glass fiber.
Comparative example 1
The preparation method of the modified glass fiber comprises the following steps:
s1, adding glass fibers into a sodium hydroxide solution with the pH of 11.5, stirring and soaking for 6min, then flushing the glass fibers to be neutral by using a mixed solution of deionized water and ethanol, and then drying the glass fibers at the temperature of 75 ℃ to obtain modified glass fibers;
the mixed solution of deionized water and ethanol refers to a uniform mixture of deionized water and ethanol according to a volume ratio of 1:1.
Other conditions were the same as in example 1.
Comparative example 2
The processing technology of the environment-friendly high heat-resistant flame-retardant modified plastic comprises the following steps:
firstly, preparing modified glass fibers;
secondly, adding starch into deionized water, stirring and dispersing to obtain starch dispersion liquid, heating to 85 ℃ to gelatinize the starch, and dehydrating and crushing to obtain modified starch;
and thirdly, uniformly mixing the modified polylactic acid, the modified starch, the epoxy resin and the modified glass fiber according to the weight ratio, and extruding the mixture through a double-screw extruder to obtain the environment-friendly high-heat-resistance flame-retardant modified plastic.
Wherein the double-screw extrusion temperature is 160 ℃, and the screw rotating speed is 100r/min;
the preparation method of the modified polylactic acid comprises the following steps:
SS1, preparing an acetic acid aqueous solution with pH value of 5, then adding hexadecyl trimethyl ammonium bromide into the aqueous solution, uniformly mixing and stirring, adding montmorillonite into the aqueous solution, stirring and dispersing, performing ultrasonic dispersion for 10min at the frequency of 120KHz, then adjusting the reaction temperature to 80 ℃, performing heat preservation reaction for 2.5h, filtering, and drying the montmorillonite at 70 ℃ to obtain organic modified montmorillonite;
and SS2, uniformly mixing the organic modified montmorillonite obtained in the step SS1 with polylactic acid according to the weight ratio of 1:12, and extruding and granulating by a double-screw extruder to obtain the modified polylactic acid, wherein the double-screw extrusion temperature is 160 ℃, and the screw rotating speed is 120r/min.
Comparative example 3
The processing technology of the environment-friendly high heat-resistant flame-retardant modified plastic comprises the following steps:
firstly, preparing modified glass fibers;
secondly, adding starch into deionized water, stirring and dispersing to obtain starch dispersion liquid, heating to 88 ℃ to gelatinize the starch, cooling the obtained gelatinized starch to 40 ℃, adding an initiator into the gelatinized starch, stirring and uniformly mixing, adding a grafting monomer into the gelatinized starch, regulating the reaction temperature to 45 ℃, stirring and reacting at constant temperature for 3 hours, and dehydrating and crushing to obtain modified starch;
wherein the initiator is cerium ammonium nitrate, and the addition amount of the initiator is 3.5% of the weight of the starch;
the grafting monomer is a uniform mixture of methyl methacrylate and vinyl acetate according to a weight ratio of 2.2:1, and the addition amount of the grafting monomer is 12% of the weight of starch;
and thirdly, uniformly mixing polylactic acid, modified starch, epoxy resin and modified glass fiber according to the weight ratio, and extruding the mixture through a double-screw extruder to obtain the environment-friendly high-heat-resistance flame-retardant modified plastic.
Wherein the twin-screw extrusion temperature is 165 ℃ and the screw rotation speed is 100r/min.
Other conditions were the same as in example 1.
Experimental data and results analysis
The materials were tested for oxygen index (GB 2406-80), impact strength (GB/T1834-1996), elongation at break (GB/T1040-92) and oxygen biodegradation rate at 37℃for 40 days, and the specific results are shown in Table 1:
TABLE 1
| Oxygen index | Impact Strength (KJ/m) 2 ) | Elongation at break (%) | Oxygen biodegradation rate (%) | |
| Example 1 | 25 | 12.9 | 8.6 | 93 |
| Example 2 | 26 | 12.7 | 9.0 | 91 |
| Comparative example 1 | 23 | 8.3 | 6.4 | 93 |
| Comparative example 2 | 25 | 9.6 | 7.1 | 96 |
| Comparative example 3 | ＜20 | 13.7 | 11.2 | 91 |
From the results, the environment-friendly high heat-resistant flame-retardant modified plastic has good impact strength and elongation at break, and has good flame retardance and degradability, so that the use anti-counterfeiting performance of polylactic acid degradable plastic is greatly improved.
The foregoing is merely illustrative of the structures of this invention and various modifications, additions and substitutions for those skilled in the art can be made to the described embodiments without departing from the scope of the invention or from the scope of the invention as defined in the accompanying claims.
Claims (5)
1. The environment-friendly high heat-resistant flame-retardant modified plastic is characterized by being prepared from the following raw materials: modified polylactic acid, modified starch, epoxy resin and modified glass fiber, wherein the weight ratio of the raw materials is that the modified polylactic acid: modified starch: epoxy resin: modified glass fiber = 100:10-55:3-7:1-3;
the environment-friendly high heat-resistant flame-retardant modified plastic is prepared by the following method:
firstly, preparing modified glass fibers;
adding starch into deionized water, stirring and dispersing to obtain starch dispersion, heating to 80-90 ℃ to gelatinize the starch, cooling the obtained gelatinized starch to 30-45 ℃, adding an initiator into the gelatinized starch, stirring and uniformly mixing, adding a grafting monomer into the gelatinized starch, regulating the reaction temperature to 40-50 ℃, stirring and reacting at constant temperature for 2-3 hours, and dehydrating and crushing to obtain modified starch;
step three, uniformly mixing modified polylactic acid, modified starch, epoxy resin and modified glass fiber according to the weight ratio, and extruding the mixture through a double-screw extruder to obtain environment-friendly high-heat-resistance flame-retardant modified plastic;
the preparation method of the modified polylactic acid comprises the following steps:
SS1, preparing an acetic acid aqueous solution with the pH value of 4.5-6, adding hexadecyl trimethyl ammonium bromide into the aqueous solution, uniformly mixing and stirring, adding montmorillonite into the aqueous solution, stirring and dispersing, performing ultrasonic dispersion for 10-13min at the frequency of 60-160KHz, adjusting the reaction temperature to 75-85 ℃, performing heat preservation reaction for 2.5-3h, filtering, and drying the montmorillonite at the temperature of 65-80 ℃ to obtain organic modified montmorillonite;
SS2, uniformly mixing the organic modified montmorillonite obtained in the step SS1 with polylactic acid according to the weight ratio of 1:9-14, and extruding and granulating by a double-screw extruder to obtain modified polylactic acid, wherein the double-screw extrusion temperature is 150-170 ℃ and the screw rotation speed is 120r/min;
the preparation method of the modified glass fiber comprises the following steps:
s1, adding nano organic montmorillonite into deionized water, wherein the weight ratio of the nano organic montmorillonite to the deionized water is 1:5-9, stirring and dispersing uniformly, freeze-drying the dispersion liquid, then adding the dispersion liquid into a ball mill, firstly dry-grinding for 5-9min under the condition of the rotating speed of 240-380r/min to crush massive organic montmorillonite, then adding the deionized water into the dispersion liquid, and continuing ball milling for 20-35min at the rotating speed to obtain montmorillonite slurry, and adding the deionized water into the montmorillonite slurry to obtain nano organic montmorillonite dispersion liquid, wherein the mass percentage of the nano organic montmorillonite is 20% -35%;
s2, preparing a water-based epoxy resin emulsion with the solid content of 18-25%, adding the water-based epoxy resin emulsion into the nano organic montmorillonite dispersion liquid in the stirring process, and after the water-based epoxy resin emulsion is completely added, increasing the stirring speed to 1600-2200r/min and stirring for 10-18min to obtain a coating liquid;
s3, adding the glass fiber into a sodium hydroxide solution with the pH of 10.5-12.5, stirring and soaking for 3-8min, then flushing with a mixed solution of deionized water and ethanol to be neutral, and then drying at the temperature of 60-90 ℃ for later use;
s4, adding the glass fiber treated in the step S3 into the coating liquid prepared in the step S2, carrying out ultrasonic treatment at the frequency of 60-100KHz for 5-10min, standing for 15-30min, taking out the glass fiber, and drying at the temperature of 65-70 ℃ after draining to obtain a glass fiber intermediate;
s5, adding the glass fiber intermediate obtained in the step S4 into a sodium hydroxide solution with the pH value of 10-11.5, soaking for 4-7min, taking out the glass fiber intermediate, washing with deionized water to be neutral, and drying at the temperature of 60-90 ℃ to obtain the modified glass fiber.
2. The environment-friendly high heat-resistant flame-retardant modified plastic as claimed in claim 1, wherein the initiator in the second step is cerium ammonium nitrate, and the addition amount of the initiator is 2% -4.5% of the weight of the starch.
3. The environment-friendly high heat-resistant flame-retardant modified plastic as claimed in claim 1, wherein the grafting monomer in the second step is a uniform mixture of methyl methacrylate and vinyl acetate according to a weight ratio of 1-2.4:1, and the addition amount of the grafting monomer is 9% -13.5% of the weight of the starch.
4. The environment-friendly high heat-resistant flame-retardant modified plastic as claimed in claim 1, wherein in the third step, the double screw extrusion temperature is 150-170 ℃ and the screw rotation speed is 100r/min.
5. The environment-friendly high heat-resistant flame-retardant modified plastic as claimed in claim 1, wherein the mixed solution of deionized water and ethanol in the step S3 is a uniform mixture of deionized water and ethanol according to a volume ratio of 1:0.3-3.
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| CN114410097A (en) * | 2021-12-28 | 2022-04-29 | 王素贞 | Recyclable engineering plastic and preparation method thereof |
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| CN101798448A (en) * | 2010-04-06 | 2010-08-11 | 奇瑞汽车股份有限公司 | Method for preparing glass fiber-reinforced flame-retardant heat-resistant polylactic acid composite material |
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