CN111875894A - Environment-friendly high-performance recycled plastic particles and preparation process thereof - Google Patents

Environment-friendly high-performance recycled plastic particles and preparation process thereof Download PDF

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CN111875894A
CN111875894A CN202010675273.1A CN202010675273A CN111875894A CN 111875894 A CN111875894 A CN 111875894A CN 202010675273 A CN202010675273 A CN 202010675273A CN 111875894 A CN111875894 A CN 111875894A
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chitosan
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张凯莉
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Jinjiang Xiangqian Shoe Material Co ltd
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    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

The invention discloses an environment-friendly high-performance recycled plastic particle which is prepared from the following raw materials in parts by weight: 50-60 parts of modified polyethylene, 30-40 parts of waste polyethylene plastic, 6-9 parts of modified chitosan, 1-1.2 parts of cross-linking agent, 0.8-1 part of reinforcing agent and 0.2-0.3 part of additive; the invention also discloses a preparation process of the regenerated plastic particles. The modified polyethylene is used as one of the regenerated plastic substrates, so that the modified polyethylene has excellent compatibility with waste plastics, and has a chemical bonding effect with modified chitosan molecules, and the antibacterial durability and the mechanical strength of the chitosan are improved; after the modified chitosan is modified, the modified chitosan can be uniformly dispersed in a polymer matrix, and the antibacterial performance of the modified chitosan is enhanced; the invention not only changes waste into valuable and meets the requirement of environmental protection, but also can obtain high-performance plastic particles with high mechanical strength and lasting, stable and antibacterial functions, and has extremely high application value in the field of plastic recovery.

Description

Environment-friendly high-performance recycled plastic particles and preparation process thereof
Technical Field
The invention belongs to the field of plastic processing, and particularly relates to an environment-friendly high-performance recycled plastic particle and a preparation process thereof.
Background
In recent years, with the continuous progress of polymer synthesis technology, the plastic industry has been rapidly developed, and more plastic products have become indispensable substances for people's life. But also brings white pollution garbage formed by a large amount of waste plastics to people and brings a large amount of resource waste and pollution control cost. Compared with the original resource development, the recycling and regeneration of the waste plastics has lower cost and can effectively reduce the pollution to the environment, so the recycling and regeneration of the waste plastics has very wide market and potential. The recycled plastic is a plastic raw material obtained by processing and processing waste plastics by physical or chemical methods such as pretreatment, melting granulation, modification and the like, and is used for recycling the plastics. However, at present, due to the types and colors of plastics, a uniform and proper pretreatment technology is difficult to achieve, so that the problems of low recovery rate of waste plastics, low quality of plastic products and the like are caused.
Chinese patent No. CN201710611502.1 discloses a method for homogenizing chain extension and recycling reclaimed plastic, which comprises removing impurities from waste plastic alkali liquor, adding polyoxyethylene and ethylene-vinyl acetate copolymer, homogenizing the waste plastic by using the amphiphilicity of the copolymer, continuously tackifying and extending chain under high pressure by further using a tackifying chain extender, and further homogenizing and extending chain to obtain high-quality reclaimed plastic. The application further homogenizes and extends the chain of the waste plastic through the chain extender, thereby improving the quality of the regenerated plastic. However, the chain extender in the application is a nano-layered inorganic particle, and the substance is an inorganic mineral particle, so that the defect of poor compatibility with a polymer matrix exists, and the phenomenon of agglomeration is easy to occur, so that the occurrence of chain extension reaction and the quality of a regenerated plastic product are influenced.
Disclosure of Invention
The invention aims to provide an environment-friendly high-performance recycled plastic particle and a preparation process thereof, wherein when waste polyethylene plastics are treated, the waste polyethylene plastics are cleaned, dried and crushed, so that impurities contained in the waste polyethylene plastics can be effectively reduced, and the waste polyethylene plastics and a polyethylene resin body have better compatibility; modified polyethylene is used as one of the regenerated plastic substrates, and benzene rings and isocyanate groups are introduced into molecular chain side chains, so that the modified polyethylene has excellent compatibility with waste plastics, and has a chemical bonding effect with modified chitosan molecules, thereby improving the antibacterial durability of chitosan and enhancing the mechanical strength of polyethylene; after the modified chitosan is modified, the modified chitosan can be uniformly dispersed in a polymer matrix, the antibacterial performance of the modified chitosan is enhanced, and the antibacterial performance is better exerted; the invention not only changes waste into valuable and meets the requirement of environmental protection, but also can obtain high-performance plastic particles with high mechanical strength and lasting, stable and antibacterial functions, and has extremely high application value in the field of plastic recovery.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly high-performance recycled plastic particle is prepared from the following raw materials in parts by weight: 50-60 parts of modified polyethylene, 30-40 parts of waste polyethylene plastic, 6-9 parts of modified chitosan, 1-1.2 parts of cross-linking agent, 0.8-1 part of reinforcing agent and 0.2-0.3 part of additive.
Further, the reinforcing agent is one or a compound of two of styrene-butadiene-styrene block copolymer and ethylene-octylene copolymer according to any mass ratio.
Further, the modified chitosan is prepared by the following method:
s1, weighing chitosan powder, adding the chitosan powder into distilled water, firstly carrying out ultrasonic treatment for 10-15min, then carrying out uniform stirring at 150r/min, slowly dropwise adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride under the stirring state, after dropwise adding, carrying out uniform stirring at 150r/min for 22-24h at room temperature, finally washing the obtained product with distilled water and methanol for 3-4 times respectively, and finally drying the product in a vacuum drying box at 60 ℃ for 20-24h to obtain grafted chitosan;
s2, dispersing the grafted chitosan in chloroform, firstly performing ultrasonic treatment for 8-10min, then adding 4g of sodium nonylphenol polyoxyethylene ether sulfate, performing magnetic stirring for 22-24h at room temperature, then adding 20mL of distilled water into a reaction system, continuing to perform magnetic stirring for 3-4h, performing suction filtration, washing the product for 4-5 times with methanol and distilled water respectively, and finally placing the product in a vacuum drying oven at 70 ℃ for drying for 20-24h to obtain the modified chitosan.
Further, the ratio of the chitosan powder, the distilled water and the dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride in the step S1 is 1g:110 and 120mL:35-40 mL.
Furthermore, the dosage ratio of the grafted chitosan, the chloroform, the sodium nonylphenol polyoxyethylene ether sulfate and the distilled water in the step S1 is 1g: 100: 150mL:10-12g:30-40 mL.
Further, the modified polyethylene is prepared by the following method:
(1) adding 1.4-1.5g of 4-vinylbenzoic acid into a round bottom flask provided with a reflux condenser tube, carrying out magnetic stirring under the condition of moisture isolation, adding 5-6mL of thionyl chloride, heating by using an oil bath, reacting for 4-5h at 65-75 ℃ until no gas is discharged, and carrying out reduced pressure evaporation on excess thionyl chloride to obtain an intermediate;
(2) adding the intermediate prepared in the step (1) and 35-40mL of toluene into a three-necked bottle, heating in an oil bath, adding 0.42-0.45g of tetrabutylammonium bromide, stirring at 60-65 ℃ for 5-6min, slowly adding 7-8g of dried sodium azide under stirring, keeping the mixture at 60-65 ℃ until no gas is generated, keeping at 78-80 ℃ for 12-15min, filtering to remove insoluble substances, and evaporating toluene under reduced pressure to obtain a modified monomer;
(3) under the protection of nitrogen, adding 1g of polyethylene and 30-40mL of toluene into a three-neck round-bottom flask provided with a condenser, a temperature controller and magnetic stirring, adding 10-12mL of modified monomer solution after the polyethylene is partially dissolved, reacting for 4-4.5h at the reaction temperature of 90 ℃, pouring the reactant into 150-200mL of acetone, violently stirring and cooling to room temperature, and filtering to obtain a crude product;
(4) dissolving the crude product in xylene, heating, refluxing and dissolving, adding a large amount of acetone, continuously stirring, repeatedly washing for 3-5 times, and finally vacuum drying at 60 ℃ for 22-24h to obtain the modified polyethylene.
Further, the modified monomer solution is a toluene solution of the modified monomer, and the mass fraction of the modified monomer solution is 20%.
A preparation process of environment-friendly high-performance recycled plastic particles comprises the following steps:
firstly, soaking waste polyethylene plastics in clear water, washing for 2-3 times by using ethanol and acetone respectively, washing for 2-3 times by using clear water, drying until the moisture content is less than 0.05%, crushing, and sieving by using a 100-mesh sieve to obtain pretreated waste polyethylene plastics;
secondly, adding the pretreated waste polyethylene, the modified chitosan, the crosslinking agent and the additive into a double-rotor continuous mixing mill, mixing at the rotor speed of 160-200r/min for 20-30min, adding the reinforcing agent, and continuously mixing for 8-10min to obtain a premix;
and step three, directly feeding the premix obtained in the step two into extrusion granulation equipment in a hot manner, and performing air exhaust, grain cutting and cooling to obtain the regenerated plastic particles.
The invention has the beneficial effects that:
the invention adds modified chitosan, and-OH and dimethyl octadecyl [3- (trimethoxy silicon base) propyl group on chitosan molecule]The silane group on the ammonium chloride molecule reacts to make dimethyl octadecyl [3- (trimethoxysilyl) propyl group]Ammonium chloride molecule is grafted onto chitosan molecule in ether bond mode, and grafted dimethyl octadecyl [3- (trimethoxysilyl) propyl group]N on ammonium chloride molecule+With SO on sodium nonylphenol ethoxylate sulfate3 -Reaction is carried out to graft nonylphenol polyoxyethylene ether sodium sulfate on dimethyl octadecyl [3- (trimethoxy silicon) propyl group]Ammonium chloride end, thereby introducing organic long-chain groups on the chitosan molecule; the organic long-chain group not only canThe compatibility of the chitosan and the polymer matrix PE is improved, the uniform dispersion of chitosan particles in the polymer matrix is promoted, the agglomeration condition among chitosan molecules can be improved, and the chitosan uniformly dispersed in the polymer matrix can not only stably exert antibacterial performance, but also serve as a stress bearing point and improve the mechanical property of the polymer matrix; in addition, after the chitosan is modified, quaternary ammonium salt molecular groups can be introduced, and the antibacterial functional groups can improve the antibacterial performance of the modified chitosan, so that the antibacterial performance of the plastic particles is further improved;
in the invention, modified polyethylene is used as one of polymer matrixes in plastic particles, and-COOH on a 4-vinylbenzoic acid molecule is firstly subjected to acyl chlorination to generate-COCl and then subjected to rearrangement reaction to generate an isocyanate group, thus obtaining a modified monomer; the prepared modified monomer molecule contains benzene ring, and para-position carbon-carbon double bond and isocyanate group, the double bond participates in copolymerization of polyethylene, modified monomer molecule is introduced into polyethylene molecular chain, namely, isocyanate group and benzene ring are introduced into side chain of polyethylene molecule, and the isocyanate group and amino-NH are introduced2OH has higher reactivity, so that the modified polyethylene can chemically react with the modified chitosan, the uniform dispersion of the modified chitosan can be promoted, the bonding force between chitosan molecules and a polymer matrix can be improved, the migration phenomenon of the chitosan is not easy to occur, and the antibacterial durability is improved; in addition, rigid benzene rings are introduced into the polyethylene molecular chains, so that the mechanical strength of the polymer matrix can be improved;
when the waste polyethylene plastic is treated, the waste polyethylene plastic is cleaned, dried and crushed, so that impurities contained in the waste polyethylene plastic can be effectively reduced, and the waste polyethylene plastic and the polyethylene resin body have better compatibility; modified polyethylene is used as one of the regenerated plastic substrates, and benzene rings and isocyanate groups are introduced into molecular chain side chains, so that the modified polyethylene has excellent compatibility with waste plastics, and has a chemical bonding effect with modified chitosan molecules, thereby improving the antibacterial durability of chitosan and enhancing the mechanical strength of polyethylene; after the modified chitosan is modified, the modified chitosan can be uniformly dispersed in a polymer matrix, the antibacterial performance of the modified chitosan is enhanced, and the antibacterial performance is better exerted; the invention not only changes waste into valuable and meets the requirement of environmental protection, but also can obtain high-performance plastic particles with high mechanical strength and lasting, stable and antibacterial functions, and has extremely high application value in the field of plastic recovery.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An environment-friendly high-performance recycled plastic particle is prepared from the following raw materials in parts by weight: 50-60 parts of modified polyethylene, 30-40 parts of waste polyethylene plastic, 6-9 parts of modified chitosan, 1-1.2 parts of cross-linking agent, 0.8-1 part of reinforcing agent and 0.2-0.3 part of additive;
the crosslinking agent is an organic peroxide, such as DCP or BPO;
the reinforcing agent is one or a compound of two of styrene-butadiene-styrene block copolymer and ethylene-octylene copolymer according to any mass ratio;
the additive is polyethylene wax;
the modified chitosan is prepared by the following method:
s1, weighing chitosan powder, adding the chitosan powder into distilled water, firstly carrying out ultrasonic treatment for 10-15min, then carrying out uniform stirring at 150r/min, slowly dropwise adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride under the stirring state, after dropwise adding, carrying out uniform stirring at 150r/min for 22-24h at room temperature, finally washing the obtained product with distilled water and methanol for 3-4 times respectively, and finally drying the product in a vacuum drying box at 60 ℃ for 20-24h to obtain grafted chitosan;
wherein the dosage ratio of the chitosan powder, the distilled water and the dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride is 1g:110-120mL:35-40 mL;
in the step, OH on the chitosan molecule reacts with silane groups on the dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride molecule, so that the dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride molecule is grafted on the chitosan molecule in an ether bond mode;
s2, dispersing the grafted chitosan in chloroform, firstly performing ultrasonic treatment for 8-10min, then adding 4g of sodium nonylphenol polyoxyethylene ether sulfate, magnetically stirring for 22-24h at room temperature, then adding 20mL of distilled water into a reaction system, continuously magnetically stirring for 3-4h, performing suction filtration, washing the product for 4-5 times with methanol and distilled water respectively, and finally drying the product in a vacuum drying oven at 70 ℃ for 20-24h to obtain modified chitosan;
wherein the dosage ratio of the grafted chitosan, the trichloromethane, the sodium nonylphenol polyoxyethylene ether sulfate and the distilled water is 1g to 100mL, 150mL to 10-12g to 30-40 mL;
-OH and dimethyl octadecyl [3- (trimethoxysilyl) propyl group on chitosan molecule]The silane group on the ammonium chloride molecule reacts to make dimethyl octadecyl [3- (trimethoxysilyl) propyl group]Ammonium chloride molecule is grafted onto chitosan molecule in ether bond mode, and grafted dimethyl octadecyl [3- (trimethoxysilyl) propyl group]N on ammonium chloride molecule+With SO on sodium nonylphenol ethoxylate sulfate3 -Reaction is carried out to graft nonylphenol polyoxyethylene ether sodium sulfate on dimethyl octadecyl [3- (trimethoxy silicon) propyl group]Ammonium chloride end, thereby introducing organic long-chain groups on the chitosan molecule; the organic long-chain group can improve the compatibility of the chitosan and the polymer matrix PE, promote the uniform dispersion of chitosan particles in the polymer matrix, improve the agglomeration condition among chitosan molecules, and ensure that the chitosan uniformly dispersed in the polymer matrix can not only stably exert antibacterial performance, but also serve as a stress bearing point and improve the mechanical property of the polymer matrix; in addition, after the chitosan is modified, quaternary ammonium salt molecular groups can be introduced, and the antibacterial functional groups can improve the antibacterial performance of the modified chitosan, so that the antibacterial performance of the plastic particles is further improved;
the modified polyethylene is prepared by the following method:
(1) adding 1.4-1.5g of 4-vinylbenzoic acid into a round bottom flask provided with a reflux condenser tube, carrying out magnetic stirring under the condition of moisture isolation, adding 5-6mL of thionyl chloride, heating by using an oil bath, reacting for 4-5h at 65-75 ℃ until no gas is discharged, and carrying out reduced pressure evaporation on excess thionyl chloride to obtain an intermediate;
in the step, reacting-COOH on 4-vinylbenzoic acid with thionyl chloride to generate acyl chloride-COCl, wherein the obtained intermediate molecule contains a carbon-carbon double bond and an acyl chloride group which are positioned at para positions;
(2) adding the intermediate prepared in the step (1) and 35-40mL of toluene into a three-necked bottle, heating in an oil bath, adding 0.42-0.45g of tetrabutylammonium bromide (phase transfer catalyst), stirring at 60-65 ℃ for 5-6min, slowly adding 7-8g of dried sodium azide under stirring, keeping the mixture at 60-65 ℃ until no gas is generated, keeping at 78-80 ℃ for 12-15min, filtering to remove insoluble substances, and evaporating toluene under reduced pressure to obtain a modified monomer;
in the step, acyl chloride groups on intermediate molecules are subjected to rearrangement reaction with sodium azide under the action of a phase transfer catalyst (tetrabutylammonium bromide) to generate isocyanate groups-NCO; the obtained modified monomer molecule contains benzene ring, carbon-carbon double bond and isocyanate group in para position;
(3) under the protection of nitrogen, adding 1g of polyethylene and 30-40mL of toluene into a three-neck round-bottom flask provided with a condenser, a temperature controller and magnetic stirring, after the polyethylene is partially dissolved, adding 10-12mL of modified monomer solution (the mass fraction of the modified monomer solution is 20%), reacting at 90 ℃ for 4-4.5h, pouring the reactant into 150 and 200mL of acetone, violently stirring and cooling to room temperature, and filtering to obtain a crude product;
(4) dissolving the crude product in xylene, heating, refluxing and dissolving, adding a large amount of acetone, continuously stirring, repeatedly washing for 3-5 times, and finally vacuum drying at 60 ℃ for 22-24 hours to obtain modified polyethylene;
firstly, acylating-COOH on the 4-vinyl benzoic acid molecule to generate-COCl, and then rearrangingReacting to generate isocyanate groups to obtain modified monomers; the prepared modified monomer molecule contains benzene ring, and para-position carbon-carbon double bond and isocyanate group, the double bond participates in copolymerization of polyethylene, modified monomer molecule is introduced into polyethylene molecular chain, namely, isocyanate group and benzene ring are introduced into side chain of polyethylene molecule, and the isocyanate group and amino-NH are introduced2OH has higher reactivity, so that the modified polyethylene can chemically react with the modified chitosan, the uniform dispersion of the modified chitosan can be promoted, the bonding force between chitosan molecules and a polymer matrix can be improved, the migration phenomenon of the chitosan is not easy to occur, and the antibacterial durability is improved; in addition, rigid benzene rings are introduced into the polyethylene molecular chains, so that the mechanical strength of the polymer matrix can be improved;
the preparation process of the environment-friendly high-performance recycled plastic particles comprises the following steps:
firstly, soaking waste polyethylene plastics in clear water, washing for 2-3 times by using ethanol and acetone respectively, washing for 2-3 times by using clear water, drying until the moisture content is less than 0.05%, crushing, and sieving by using a 100-mesh sieve to obtain pretreated waste polyethylene plastics;
secondly, adding the pretreated waste polyethylene, the modified chitosan, the crosslinking agent and the additive into a double-rotor continuous mixing mill, mixing at the rotor speed of 160-200r/min for 20-30min, adding the reinforcing agent, and continuously mixing for 8-10min to obtain a premix;
and step three, directly feeding the premix obtained in the step two into extrusion granulation equipment in a hot manner, and performing air exhaust, grain cutting and cooling to obtain the regenerated plastic particles.
Example 1
The modified chitosan is prepared by the following method:
s1, weighing chitosan powder, adding the chitosan powder into distilled water, firstly carrying out ultrasonic treatment for 10min, then carrying out uniform stirring at 150r/min, slowly dropwise adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride under the stirring state, after dropwise adding, carrying out uniform stirring at 150r/min for 22h at room temperature, finally washing the obtained product for 3 times respectively by using distilled water and methanol, and finally drying the product in a vacuum drying oven at 60 ℃ for 20h to obtain grafted chitosan;
wherein the dosage ratio of the chitosan powder, the distilled water and the dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride is 1g:110mL:35 mL;
s2, dispersing grafted chitosan in chloroform, firstly performing ultrasonic treatment for 8min, then adding 4g of sodium nonylphenol polyoxyethylene ether sulfate, performing magnetic stirring for 22h at room temperature, then adding 20mL of distilled water into a reaction system, continuing to perform magnetic stirring for 3h, performing suction filtration, washing the product for 4 times with methanol and distilled water respectively, and finally drying the product in a vacuum drying oven at 70 ℃ for 20h to obtain modified chitosan;
wherein the dosage ratio of the grafted chitosan, the trichloromethane, the sodium nonylphenol polyoxyethylene ether sulfate and the distilled water is 1g:100mL:10g:30 mL.
Example 2
The modified chitosan is prepared by the following method:
s1, weighing chitosan powder, adding the chitosan powder into distilled water, firstly carrying out ultrasonic treatment for 15min, then carrying out uniform stirring at 150r/min, slowly dropwise adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride under the stirring state, after dropwise adding, carrying out uniform stirring at 150r/min for 24h at room temperature, finally washing the obtained product for 4 times respectively by using distilled water and methanol, and finally drying the product in a vacuum drying box at 60 ℃ for 24h to obtain the grafted chitosan;
wherein the dosage ratio of the chitosan powder, the distilled water and the dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride is 1g:120mL:40 mL;
s2, dispersing grafted chitosan in chloroform, firstly performing ultrasonic treatment for 10min, then adding 4g of sodium nonylphenol polyoxyethylene ether sulfate, magnetically stirring for 24h at room temperature, then adding 20mL of distilled water into a reaction system, continuously magnetically stirring for 4h, performing suction filtration, washing a product for 5 times by using methanol and distilled water respectively, and finally drying the product in a vacuum drying oven at 70 ℃ for 24h to obtain modified chitosan;
wherein the dosage ratio of the grafted chitosan, the trichloromethane, the sodium nonylphenol polyoxyethylene ether sulfate and the distilled water is 1g:150mL:12g:40 mL.
Comparative example 1
And (3) chitosan powder.
Example 3
The modified polyethylene is prepared by the following method:
(1) adding 1.4g of 4-vinyl benzoic acid into a round bottom flask with a reflux condenser tube, carrying out magnetic stirring under the condition of moisture isolation, adding 5mL of thionyl chloride, heating by using an oil bath, reacting for 5 hours at 65 ℃ until no gas is discharged, and distilling out excessive thionyl chloride under reduced pressure to obtain an intermediate;
(2) adding the intermediate prepared in the step (1) and 35mL of toluene into a three-necked bottle, heating in an oil bath, adding 0.42g of tetrabutylammonium bromide, stirring at 60 ℃ for 5min, slowly adding 7g of dried sodium azide under stirring, keeping the mixture at 60 ℃ until no gas is generated, keeping at 78 ℃ for 12min, filtering to remove insoluble substances, and evaporating toluene under reduced pressure to obtain a modified monomer;
(3) under the protection of nitrogen, 1g of polyethylene and 30mL of toluene are added into a three-neck round-bottom flask provided with a condenser, a temperature controller and magnetic stirring, after the polyethylene is partially dissolved, 10mL of modified monomer solution (the modified monomer toluene solution accounts for 20 mass percent) is added, the reaction temperature is 90 ℃, the reaction is carried out for 4 hours, reactants are poured into 150mL of acetone, the mixture is vigorously stirred and cooled to the room temperature, and the crude product is obtained after filtration;
(4) and dissolving the crude product in xylene, heating, refluxing and dissolving, adding a large amount of acetone, continuously stirring, repeatedly washing for 3 times, and finally vacuum-drying at 60 ℃ for 22 hours to obtain the modified polyethylene.
Example 4
The modified polyethylene is prepared by the following method:
(1) adding 1.5g of 4-vinyl benzoic acid into a round bottom flask with a reflux condenser tube, carrying out magnetic stirring under the condition of moisture isolation, adding 6mL of thionyl chloride, heating by using an oil bath, reacting for 4 hours at 75 ℃ until no gas is discharged, and distilling out excessive thionyl chloride under reduced pressure to obtain an intermediate;
(2) adding the intermediate prepared in the step (1) and 40mL of toluene into a three-necked bottle, heating in an oil bath, adding 0.42g of tetrabutylammonium bromide, stirring at 65 ℃ for 6min, slowly adding 8g of dried sodium azide under stirring, keeping the mixture at 65 ℃ until no gas is generated, keeping at 80 ℃ for 15min, filtering to remove insoluble substances, and evaporating toluene under reduced pressure to obtain a modified monomer;
(3) under the protection of nitrogen, 1g of polyethylene and 40mL of toluene are added into a three-neck round-bottom flask provided with a condenser, a temperature controller and magnetic stirring, after the polyethylene is partially dissolved, 12mL of modified monomer solution (the modified monomer toluene solution accounts for 20 mass percent) is added, the reaction temperature is 90 ℃, the reaction is carried out for 4.5 hours, reactants are poured into 200mL of acetone, the mixture is vigorously stirred and cooled to the room temperature, and the crude product is obtained after filtration;
(4) and dissolving the crude product in xylene, heating, refluxing and dissolving, adding a large amount of acetone, continuously stirring, repeatedly washing for 5 times, and finally vacuum-drying at 60 ℃ for 24 hours to obtain the modified polyethylene.
Comparative example 2
A polyethylene resin.
Example 5
An environment-friendly high-performance recycled plastic particle is prepared from the following raw materials in parts by weight: 50 parts of modified polyethylene prepared in example 3, 30 parts of waste polyethylene plastic, 6 parts of modified chitosan prepared in example 1, 1 part of cross-linking agent, 0.8 part of reinforcing agent and 0.2 part of additive;
the recycled plastic particles are prepared by the following steps:
firstly, soaking waste polyethylene plastics in clear water, washing the waste polyethylene plastics with ethanol and acetone for 2 times respectively, washing the waste polyethylene plastics with clear water for 2 times, drying the waste polyethylene plastics until the moisture content is less than 0.05 percent, crushing the waste polyethylene plastics and sieving the crushed waste polyethylene plastics with a 100-mesh sieve to obtain pretreated waste polyethylene plastics;
secondly, adding the pretreated waste polyethylene, the modified polyethylene prepared in the embodiment 3, the modified chitosan prepared in the embodiment 1, the cross-linking agent and the additive into a double-rotor continuous mixing mill, mixing at the rotor speed of 160r/min for 30min, adding the reinforcing agent, and continuously mixing for 8min to obtain a premix;
and step three, directly feeding the premix obtained in the step two into extrusion granulation equipment in a hot manner, and performing air exhaust, grain cutting and cooling to obtain the regenerated plastic particles.
Example 6
An environment-friendly high-performance recycled plastic particle is prepared from the following raw materials in parts by weight: 55 parts of modified polyethylene prepared in example 4, 35 parts of waste polyethylene plastic, 7.5 parts of modified chitosan prepared in example 2, 1.1 parts of cross-linking agent, 0.9 part of reinforcing agent and 0.25 part of additive;
the recycled plastic particles are prepared by the following steps:
firstly, soaking waste polyethylene plastics in clear water, washing for 3 times by using ethanol and acetone respectively, washing for 3 times by using clear water, drying until the moisture content is less than 0.05%, crushing, and sieving by using a 100-mesh sieve to obtain pretreated waste polyethylene plastics;
secondly, adding the pretreated waste polyethylene, the modified polyethylene prepared in the embodiment 4, the modified chitosan prepared in the embodiment 2, the cross-linking agent and the additive into a double-rotor continuous mixing mill, mixing at the rotor speed of 180r/min for 25min, adding the reinforcing agent, and continuously mixing for 9min to obtain a premix;
and step three, directly feeding the premix obtained in the step two into extrusion granulation equipment in a hot manner, and performing air exhaust, grain cutting and cooling to obtain the regenerated plastic particles.
Example 7
An environment-friendly high-performance recycled plastic particle is prepared from the following raw materials in parts by weight: 60 parts of modified polyethylene prepared in example 3, 40 parts of waste polyethylene plastic, 9 parts of modified chitosan prepared in example 1, 1.2 parts of cross-linking agent, 1 part of reinforcing agent and 0.3 part of additive;
the recycled plastic particles are prepared by the following steps:
firstly, soaking waste polyethylene plastics in clear water, washing for 3 times by using ethanol and acetone respectively, washing for 3 times by using clear water, drying until the moisture content is less than 0.05%, crushing, and sieving by using a 100-mesh sieve to obtain pretreated waste polyethylene plastics;
secondly, adding the pretreated waste polyethylene, the modified polyethylene prepared in the embodiment 3, the modified chitosan prepared in the embodiment 1, the cross-linking agent and the additive into a double-rotor continuous mixing mill, mixing at the rotor speed of 200r/min for 20min, adding the reinforcing agent, and continuously mixing for 10min to obtain a premix;
and step three, directly feeding the premix obtained in the step two into extrusion granulation equipment in a hot manner, and performing air exhaust, grain cutting and cooling to obtain the regenerated plastic particles.
Comparative example 3
The modified polyethylene in example 5 was replaced with the polyethylene resin of comparative example 2, and the remaining raw materials and preparation process were unchanged.
Comparative example 4
The modified chitosan in example 5 was replaced with the chitosan powder of comparative example 1, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 5
Polyethylene resin particles.
The plastic particles prepared in examples 5-7 and comparative examples 3-5 were blown into plastic films on a film blowing machine in the same manner, and film samples of the same specification were taken for the following performance tests:
measuring the tensile strength and the elongation at break according to GB/T1040-; the impact strength is tested according to GB/T1843-2008; testing the bacteriostasis rate of the film on escherichia coli and staphylococcus aureus by referring to QB/T2591-2003; the test results are shown in the following table:
Figure BDA0002583817780000141
as can be seen from the above table, the films obtained in examples 5 to 7 had tensile strengths of 26.99 to 28.32MPa, elongations at break of 240-250% and impact strengths of 102.4 to 103.3 kJ. m-2Compared with pure polyethylene resin, the regenerated plastic particles prepared by the method have higher mechanical strength; as can be seen from the above table, the antibacterial rate of the film prepared in examples 5-7 to the large intestine feeling is 98.2-98.5%, and the antibacterial rate to Staphylococcus aureus is 97.9-98.3%, which indicates that the regenerated plastic granules prepared by the invention have good antibacterial performance, and after 18 months, the film has good antibacterial performanceThe decrease range of the antibacterial rate is very small, and is 0.3-0.4%, which shows that the regenerated plastic particles prepared by the invention also have the characteristic of antibacterial durability; by combining the comparative example 3 and the comparative example 4, the modified polyethylene can introduce benzene rings and isocyanate groups on molecular side chains, the introduction of the benzene rings can improve the mechanical strength of the plastic, and the introduction of the isocyanate groups can enable the modified chitosan and the polymer matrix to generate chemical bonding effect, so that the antibacterial durability is improved; compared with comparative example 4, the modified chitosan can not only increase the antibacterial performance of the chitosan to further enhance the antibacterial capability of the regenerated plastic, but also can be more uniformly distributed in the polymer matrix to fully exert the antibacterial performance.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (8)

1. The environment-friendly high-performance recycled plastic particle is characterized by being prepared from the following raw materials in parts by weight: 50-60 parts of modified polyethylene, 30-40 parts of waste polyethylene plastic, 6-9 parts of modified chitosan, 1-1.2 parts of cross-linking agent, 0.8-1 part of reinforcing agent and 0.2-0.3 part of additive.
2. The environment-friendly high-performance recycled plastic granules as claimed in claim 1, wherein the reinforcing agent is one or a mixture of styrene-butadiene-styrene block copolymer and ethylene-octylene copolymer in any mass ratio.
3. The environment-friendly high-performance recycled plastic particle as claimed in claim 1, wherein the modified chitosan is prepared by the following method:
s1, weighing chitosan powder, adding the chitosan powder into distilled water, firstly carrying out ultrasonic treatment for 10-15min, then carrying out uniform stirring at 150r/min, slowly dropwise adding dimethyl octadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride under the stirring state, after dropwise adding, carrying out uniform stirring at 150r/min for 22-24h at room temperature, finally washing the obtained product with distilled water and methanol for 3-4 times respectively, and finally drying the product in a vacuum drying box at 60 ℃ for 20-24h to obtain grafted chitosan;
s2, dispersing the grafted chitosan in chloroform, firstly performing ultrasonic treatment for 8-10min, then adding 4g of sodium nonylphenol polyoxyethylene ether sulfate, performing magnetic stirring for 22-24h at room temperature, then adding 20mL of distilled water into a reaction system, continuing to perform magnetic stirring for 3-4h, performing suction filtration, washing the product for 4-5 times with methanol and distilled water respectively, and finally placing the product in a vacuum drying oven at 70 ℃ for drying for 20-24h to obtain the modified chitosan.
4. The recycled plastic pellet as claimed in claim 3, wherein the ratio of the chitosan powder, distilled water and dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride in step S1 is 1g: 110: 120mL:35-40 mL.
5. The recycled plastic granules with environmental protection and high performance as claimed in claim 3, wherein the ratio of the amounts of the grafted chitosan, chloroform, sodium nonylphenol polyoxyethylene ether sulfate and distilled water in step S1 is 1g: 100: 150mL:10-12g:30-40 mL.
6. The environment-friendly high-performance recycled plastic granules according to claim 1, wherein the modified polyethylene is prepared by the following method:
(1) adding 1.4-1.5g of 4-vinylbenzoic acid into a round bottom flask provided with a reflux condenser tube, carrying out magnetic stirring under the condition of moisture isolation, adding 5-6mL of thionyl chloride, heating by using an oil bath, reacting for 4-5h at 65-75 ℃ until no gas is discharged, and carrying out reduced pressure evaporation on excess thionyl chloride to obtain an intermediate;
(2) adding the intermediate prepared in the step (1) and 35-40mL of toluene into a three-necked bottle, heating in an oil bath, adding 0.42-0.45g of tetrabutylammonium bromide, stirring at 60-65 ℃ for 5-6min, slowly adding 7-8g of dried sodium azide under stirring, keeping the mixture at 60-65 ℃ until no gas is generated, keeping at 78-80 ℃ for 12-15min, filtering to remove insoluble substances, and evaporating toluene under reduced pressure to obtain a modified monomer;
(3) under the protection of nitrogen, adding 1g of polyethylene and 30-40mL of toluene into a three-neck round-bottom flask provided with a condenser, a temperature controller and magnetic stirring, adding 10-12mL of modified monomer solution after the polyethylene is partially dissolved, reacting for 4-4.5h at the reaction temperature of 90 ℃, pouring the reactant into 150-200mL of acetone, violently stirring and cooling to room temperature, and filtering to obtain a crude product;
(4) dissolving the crude product in xylene, heating, refluxing and dissolving, adding a large amount of acetone, continuously stirring, repeatedly washing for 3-5 times, and finally vacuum drying at 60 ℃ for 22-24h to obtain the modified polyethylene.
7. The environment-friendly high-performance recycled plastic granules as claimed in claim 6, wherein the modified monomer solution is a toluene solution of modified monomer, and the mass fraction is 20%.
8. The preparation process of the environment-friendly high-performance recycled plastic granules according to claim 1, characterized by comprising the following steps:
firstly, soaking waste polyethylene plastics in clear water, washing for 2-3 times by using ethanol and acetone respectively, washing for 2-3 times by using clear water, drying until the moisture content is less than 0.05%, crushing, and sieving by using a 100-mesh sieve to obtain pretreated waste polyethylene plastics;
secondly, adding the pretreated waste polyethylene, the modified chitosan, the crosslinking agent and the additive into a double-rotor continuous mixing mill, mixing at the rotor speed of 160-200r/min for 20-30min, adding the reinforcing agent, and continuously mixing for 8-10min to obtain a premix;
and step three, directly feeding the premix obtained in the step two into extrusion granulation equipment in a hot manner, and performing air exhaust, grain cutting and cooling to obtain the regenerated plastic particles.
CN202010675273.1A 2020-07-14 2020-07-14 Environment-friendly high-performance recycled plastic particles and preparation process thereof Pending CN111875894A (en)

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