CN110483695B - Cardanol grafted high-density polyethylene synthesized by reactive extrusion and application thereof in bamboo-plastic composite material - Google Patents
Cardanol grafted high-density polyethylene synthesized by reactive extrusion and application thereof in bamboo-plastic composite material Download PDFInfo
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Abstract
The invention discloses cardanol grafted high-density polyethylene synthesized by reactive extrusion and application thereof in bamboo-plastic composite materials, wherein the cardanol grafted high-density polyethylene comprises the following steps: a. preparing cardanol grafted high-density polyethylene by reactive extrusion: dissolving composite initiators, namely Lauroyl Peroxide (LPO) and dibenzoyl peroxide (BPO), in cardanol, adding the cardanol into high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding by using an extruder, and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene; b. the application of cardanol grafted high-density polyethylene by reactive extrusion comprises the following steps: uniformly stirring and mixing the cardanol grafted high-density polyethylene prepared in the step a) with bamboo powder and plastic at a high speed, and then extruding, injecting or hot-press molding to obtain the bamboo-plastic composite material. The cardanol grafted high-density polyethylene free radical extruded by the composite initiator through reaction has stable concentration, low processing temperature, no need of purification of products and high grafting rate, and can be used as a plastic matrix or a coupling agent of the bamboo-plastic composite material to prevent thermal degradation of bamboo powder.
Description
Technical Field
The invention relates to cardanol grafted high-density polyethylene synthesized by reaction extrusion, and belongs to the technical field of general high polymer materials.
Background
The wood-plastic composite material has good processing performance, can be used for sawing, nailing and planing woodworker tools, has better mechanical properties such as compression resistance, bending resistance and the like than wood materials, has excellent water resistance, corrosion resistance and adjustment performance, and is a novel composite material which is brisk in recent years at home and abroad. The wood-plastic composite material is mainly prepared by mixing polyethylene, polypropylene, polyvinyl chloride and the like instead of a common resin adhesive with more than 50% of waste plant fibers such as wood flour, rice hulls, straws and the like to form a new wood material, and then carrying out plastic processing processes such as extrusion, die pressing, injection molding and the like. However, hydrophobic polyethylene and hydrophilic fibers have weak interfacial adhesion, and in order to enhance the interfacial adhesion, a coupling agent is often added or the polyethylene and the fibers are subjected to surface modification, wherein the effect of grafting polar monomer thermoplastic elastomers or polyolefins is better. At present, maleic anhydride is often used as a polar monomer to obtain maleic anhydride grafted polyolefin by a reactive extrusion method, but the maleic anhydride monomer volatilized in the reactive extrusion process is corrosive and can cause damage to machines and human bodies; secondly, the product contains unreacted monomers which are difficult to purify, and the performance of the product is influenced; thirdly, the polyolefin molecular main chain can generate side reactions such as degradation, crosslinking and the like under the action of an initiator in the reaction process.
Cardanol, which is a main component of a natural cashew nut shell squeezing liquid, is a monophenol derivative having an unsaturated long-side carbon chain. The long unsaturated side carbon chain can generate addition polymerization reaction, the phenolic hydroxyl group on the benzene ring enables cardanol to have certain polarity, esterification reaction, etherification reaction, oxidation reaction and coordination reaction can be carried out, and the condensation polymerization reaction, nitration reaction, sulfonation reaction, halogenation reaction, Friedel-Crafts reaction, vulcanization reaction, azo reaction and the like of phenolic compounds can also be carried out. Cardanol is introduced to a polyolefin main chain, so that the surface energy of polyolefin can be increased, and the reaction functional group of the polyolefin is increased. The influence of initiator types on the reaction extrusion polypropylene grafted cardanol, the influence of bulnesia, buerger-dun and the like on the structure and the performance of a product are researched in ' the influence of initiator types on the reaction extrusion polypropylene grafted cardanol ', ' the process optimization, the aging performance and the compatibilization of the reaction extrusion polypropylene grafted cardanol ', ' the influence of rare earth oxide on the reaction extrusion polypropylene grafted cardanol ' and ' the influence of processing technology on the reaction extrusion cardanol grafted polypropylene ' of forest construction boon ' (Chinese plastics, 2016, 30 (5): 71) ') and ' the influence of a swivel nut combination on the reaction extrusion polypropylene grafted cardanol ' (Fujian-Shi university report (Nature science edition), 2018, 34 (2): 28) '. Under the optimal temperature of reaction extrusion of 180 ℃, the polypropylene main chain is not degraded basically under the stabilizing effect of cardanol phenolic hydroxyl on free radicals. However, the initiator DCP used in the reaction has a high decomposition temperature (120-125 ℃) and a decomposition temperature of 165 ℃ with a half-life of 1 minute. The screw barrel of the double-screw extruder is a high-temperature, high-pressure and high-viscosity place, the processes of mass transfer, heat transfer and pressure transfer are different from those of general reaction places, and the reaction extrusion is a continuous process, so that the material stays in the screw barrel for a short time. Therefore, the single DCP initiator is not decomposed immediately after entering the screw cylinder due to the high initiated decomposition temperature, the grafting reaction cannot be carried out, once the DCP starts to be decomposed, the DCP is affected by the difficulty in the mass and heat transfer process, the local free radical concentration of the DCP initiator is high, the polyolefin is easy to be degraded and subjected to crosslinking side reaction, and the grafting reaction cannot be initiated efficiently. Therefore, when the cardanol grafted high-density polyethylene is prepared, lauroyl peroxide (with the decomposition temperature of 70-80 ℃) and dibenzoyl peroxide (with the decomposition temperature of 105 ℃) with the half-life of 1 minute and the decomposition temperatures of 115 ℃ and 133 ℃ respectively are selected to be compounded as an initiator, and the cardanol grafted high-density polyethylene is prepared through reaction, extrusion and synthesis at a low processing temperature. The lower processing temperature can reduce energy consumption and thermal degradation of the bamboo powder; the composite initiator can keep the concentration of free radicals in each section of the screw cylinder at a stable level, prolong the grafting reaction time and improve the grafting reaction efficiency, and has important application value for obtaining the bamboo-plastic composite material with excellent processing performance and mechanical performance.
Disclosure of Invention
The invention aims to overcome the defects of using a single DCP initiator for reactive extrusion of cardanol grafted polypropylene, and provides a method for reactive extrusion of cardanol grafted high-density polyethylene, which uses a composite initiator, keeps the concentration of free radicals in a screw cylinder stable, prolongs the reaction time and improves the grafting rate.
The invention is realized by the following technical scheme:
a. preparing cardanol grafted high-density polyethylene by reactive extrusion:
dissolving a composite initiator Lauroyl Peroxide (LPO) and dibenzoyl peroxide (BPO) in cardanol, adding the cardanol into high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding at the temperature of 140-170 ℃ by using an extruder, and performing water cooling and granulation to obtain a reaction extrusion product, namely the high-density polyethylene grafted cardanol;
wherein the mass parts of the HDPE, the cardanol, the LPO and the BPO are 100: 1-20: 0.01-1;
b. the application of cardanol grafted high-density polyethylene by reactive extrusion comprises the following steps:
uniformly stirring and mixing the cardanol grafted high-density polyethylene and bamboo powder (the cardanol grafted high-density polyethylene is used as a plastic substrate) or the cardanol grafted high-density polyethylene, the bamboo powder and the plastic (the cardanol grafted high-density polyethylene is used as a coupling agent) at a high speed, and extruding, injection molding or hot press molding at a temperature of 20-30 ℃ above the melting point of the plastic by using an extruder to obtain a bamboo-plastic composite material;
the cardanol grafted high-density polyethylene, the bamboo powder and the plastic are in a ratio of 1-100: 1-70: 0-100 in parts by mass.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses the composite initiator, the first material enters a double-screw extruder, the lauroyl peroxide is firstly decomposed to provide free radicals, the concentration of the lauroyl peroxide is reduced along with the forward conveying of the materials, the temperature of the materials is increased, the dibenzoyl peroxide starts to be decomposed to supplement the free radicals until the materials leave a screw cylinder, the two initiators both have half-life periods, the concentration of the free radicals in the screw cylinder is kept at a stable level, the materials are maintained to carry out grafting reaction in the whole process in the screw cylinder, and the grafting rate of the product is improved.
2. The reaction extrusion method disclosed by the invention has the advantages that the temperature for synthesizing the high-density polyethylene grafted fruit phenol is lower, the processing temperature for compounding the high-density polyethylene grafted fruit phenol with the bamboo powder is also lower, and the thermal degradation of the bamboo powder can be effectively prevented.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a transmission micrograph (50 times magnification) of a cardanol grafted high density polyethylene/bamboo powder composite prepared in example 1 of the present invention.
Fig. 2 is a scanning electron micrograph (magnification 200 times) of a brittle section of the cardanol grafted high density polyethylene/bamboo powder composite material prepared in example 1 of the present invention.
Detailed Description
Example 1
Step one
Dissolving 1g of Lauroyl Peroxide (LPO) and 1g of dibenzoyl peroxide (BPO) in 70g of cardanol, adding the cardanol into 1000g of high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding by using a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are 150 ℃, 160 ℃, 170 ℃ and 160 ℃) respectively, and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene (the grafting rate is 6.82%);
step two
Stirring and mixing 1000g of cardanol grafted high-density polyethylene and 300g of bamboo powder at a high speed, and then extruding by using a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are 150 ℃, 160 ℃, 170 ℃ and 160 ℃ respectively) to obtain a bamboo-plastic composite material;
FIG. 1 is a transmission micrograph showing that the bamboo powder in the cardanol grafted high density polyethylene/bamboo powder composite is distributed very uniformly in the plastic matrix; FIG. 2 is a scanning electron micrograph of a brittle section of a cardanol grafted high-density polyethylene/bamboo powder composite material, which shows that a plastic substrate and bamboo powder are tightly combined under the coupling effect of cardanol groups on the surface of high-density polyethylene.
Example 2
Step one
Dissolving 0.1g of Lauroyl Peroxide (LPO) and 2g of dibenzoyl peroxide (BPO) in 150g of cardanol, adding the cardanol into 1000g of high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding by using a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are respectively 150 ℃, 160 ℃, 170 ℃ and 160 ℃), and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene (the grafting ratio is 4.73%);
step two
And (3) stirring and mixing 1000g of cardanol grafted high-density polyethylene and 700g of bamboo powder uniformly at a high speed, and carrying out hot pressing at 160 ℃ by using a hot press to obtain the bamboo-plastic composite material.
Example 3
Step one
Dissolving 2g of Lauroyl Peroxide (LPO) and 0.1g of dibenzoyl peroxide (BPO) in 70g of cardanol, adding the cardanol into 1000g of high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding by using a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are respectively 140 ℃, 150 ℃ and 140 ℃), and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene (the grafting ratio is 4.27%);
step two
Stirring and mixing 1000g of cardanol grafted high-density polyethylene and 500g of bamboo powder uniformly at a high speed, and extruding by using an injection molding machine (the heating temperature is 150 ℃, 160 ℃ and 170 ℃ from a feed inlet respectively) to obtain the bamboo-plastic composite material.
Example 4
Step one
Dissolving 5g of Lauroyl Peroxide (LPO) and 5g of dibenzoyl peroxide (BPO) in 80g of cardanol, adding the cardanol into 1000g of high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding by using a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are 160 ℃, 160 ℃ and 150 ℃) respectively, and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene (the grafting rate is 5.57%);
step two
100g of cardanol grafted high-density polyethylene, 300g of bamboo powder and 1000g of polypropylene are stirred and mixed uniformly at a high speed, and then the mixture is extruded by a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are respectively 180 ℃, 190 ℃, 200 ℃ and 190 ℃) to obtain the bamboo-plastic composite material.
Example 5
Step one
Dissolving 3g of Lauroyl Peroxide (LPO) and 7g of dibenzoyl peroxide (BPO) in 200g of cardanol, adding the cardanol into 1000g of high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding by using a double-screw extruder (the temperatures of a solid conveying section, a melting section, a reaction mixing section and a melt conveying section of the extruder are 160 ℃, 170 ℃ and 150 ℃) respectively, and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene (the grafting rate is 8.44%);
step two
100g of cardanol grafted high-density polyethylene, 1000g of bamboo powder and 1000g of polyvinyl chloride are stirred at a high speed and mixed uniformly, and then a hot press is used for hot pressing at the temperature of 190 ℃ to obtain the bamboo-plastic composite material.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. The cardanol grafted high-density polyethylene is characterized in that the cardanol grafted high-density polyethylene is prepared by reacting and extruding materials containing lauroyl peroxide, dibenzoyl peroxide, cardanol and high-density polyethylene.
2. The preparation method of cardanol grafted high-density polyethylene according to claim 1, characterized by comprising at least the following steps:
dissolving a composite initiator Lauroyl Peroxide (LPO) and dibenzoyl peroxide (BPO) in cardanol, adding the cardanol into high-density polyethylene (HDPE) resin, stirring at a high speed, uniformly mixing, extruding at the temperature of 140-170 ℃ by using an extruder, and performing water cooling and granulation to obtain a reaction extrusion product, namely cardanol grafted high-density polyethylene.
3. The preparation method of cardanol grafted high-density polyethylene according to claim 2, wherein the mass ratio of HDPE, cardanol, LPO and BPO is 100: 1-20: 0.01-1.
4. The cardanol grafted high-density polyethylene according to claim 1, wherein the cardanol grafted high-density polyethylene is applied to a bamboo-plastic composite material.
5. The application of cardanol grafted high-density polyethylene in bamboo-plastic composite materials as claimed in claim 4, wherein the cardanol grafted high-density polyethylene comprises the following steps:
uniformly stirring and mixing the cardanol grafted high-density polyethylene and bamboo powder or the cardanol grafted high-density polyethylene, the bamboo powder and the plastic at a high speed, extruding by using an extruder at a temperature of 20-30 ℃ above the melting point of the plastic, and performing injection molding or hot press molding to obtain a bamboo-plastic composite material;
the cardanol grafted high-density polyethylene, the bamboo powder and the plastic are in a ratio of 1-100: 1-70: 0-100 in parts by mass.
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| CN113024814B (en) * | 2021-03-15 | 2022-06-07 | 湖南工业大学 | Bio-based polysiloxane scratch-resistant auxiliary agent, preparation method thereof and scratch-resistant composite material |
| CN113337028B (en) * | 2021-07-20 | 2023-04-28 | 福建师范大学泉港石化研究院 | Plastic wall pipe and manufacturing method thereof |
| CN115537960B (en) * | 2022-11-09 | 2023-09-15 | 福建师范大学泉港石化研究院 | Modified tourmaline polypropylene melt-blown material and preparation method and application thereof |
| CN115537964B (en) * | 2022-11-09 | 2023-09-15 | 福建师范大学泉港石化研究院 | Modified tourmaline polylactic acid melt-blown material and preparation method and application thereof |
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| WO2014087801A1 (en) * | 2012-12-07 | 2014-06-12 | 日本電気株式会社 | Cellulose resin composition and use of same |
| CN107298783A (en) * | 2017-06-29 | 2017-10-27 | 苏州安特实业有限公司 | A kind of preparation method of the composite modified polyethylene packaging material of chitosan/anacardol |
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