CN110791013A - Polymer plastic for processing plastic pencil holder - Google Patents
Polymer plastic for processing plastic pencil holder Download PDFInfo
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- CN110791013A CN110791013A CN201910973169.8A CN201910973169A CN110791013A CN 110791013 A CN110791013 A CN 110791013A CN 201910973169 A CN201910973169 A CN 201910973169A CN 110791013 A CN110791013 A CN 110791013A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
- B43K19/02—Pencils with graphite; Coloured pencils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K3/00—Nib holders
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/052—Inducing phase separation by thermal treatment, e.g. cooling a solution
- C08J2201/0522—Inducing phase separation by thermal treatment, e.g. cooling a solution the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
Abstract
The invention discloses a polymer plastic for processing a plastic pencil shaft, which comprises the following specific preparation methods: 1) performing modification treatment on chitosan to obtain modified chitosan; 2) preparing a nano titanium dioxide/modified chitosan compound by using the modified chitosan and the nano titanium dioxide, and then adding graphene oxide to prepare a graphene oxide/nano titanium dioxide/modified chitosan compound; 3) preparing polylactic acid porous microspheres; 4) preparing porous composite microspheres by using the porous microspheres and the compound in the step 2); 5) and stirring the porous composite microspheres and the raw materials to obtain a mixture, then putting the mixture into an extruder, and extruding and granulating to obtain the polymer plastic. The polymer plastic is used as a raw material to prepare the plastic pencil holder, so that the coiling and cutting resistance of the plastic pencil can be effectively reduced, the plastic pencil holder is easy to coil and cut, the compact structure of a coiling and cutting surface can be kept, the coiling and cutting surface is not easy to be stained, and the neatness and the attractiveness of the plastic pencil are improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to polymer plastic for processing a plastic pencil shaft.
Background
The traditional pencil holder is mainly made of wood, but the method has higher requirements on wood, only effective tree species wood such as red cedar, basswood, camauba and the like can be suitable, the application and development of the pencil holder are severely restricted, the waste of resources is easily caused, and the pencil holder does not meet the requirements on environmental protection at present. Based on the wide application and development of the plastic pen holder replacing the wood pen holder, the plastic pen holder can not only solve the waste of wood resources and meet the requirement of environmental protection, but also has low cost and high economic benefit.
However, the existing plastic penholder has large coiling and cutting resistance, and the coiling and cutting resistance is seriously not in line with the requirement especially on special occasions for children, so that the plastic penholder is not beneficial to the use of the children. Therefore, the technical problems to be solved urgently by the technical personnel in the field are to reduce the coiling and cutting resistance of the plastic penholder and the coiling and cutting difficulty of children. In the prior art, the polymer plastic of the plastic penholder is foamed, so that the coiling and cutting resistance of the plastic penholder can be effectively reduced, the coiling and cutting difficulty of children is reduced, and the plastic pencil is suitable for children. For example, chinese patent nos. CN108997677A and CN1204008C both adopt a method of foaming a plastic pencil holder to reduce the curling resistance of the plastic pencil holder, but through foaming, the phenomena of non-fine foaming and non-uniform pores are likely to occur, resulting in an imperfect appearance of the plastic pencil, and through foaming, a large number of pores are distributed on the curling surface of the plastic pencil, and a large amount of dust and stains are adsorbed, and adhered in the pores, and are not easy to be removed, thereby reducing the beauty of the curling surface of the plastic pencil.
Disclosure of Invention
The invention aims to solve the existing problems and provides a polymer plastic for processing a plastic pencil holder, which has low coiling and cutting resistance and compact coiling and cutting surface structure, and is not easy to be stained with dust and stains, so that the coiling and cutting surface can be kept clean for a long time, and the attractiveness of a plastic pencil is effectively improved.
The invention is realized by the following technical scheme:
the polymer plastic for processing the plastic pencil shaft is characterized by being prepared by the following specific steps:
1) sequentially adding chitosan, isopropanol, a sodium hydroxide solution and chloroacetic acid into a reactor, heating to 50-60 ℃, reacting for 6-8h, continuously adding the sodium hydroxide solution and triethyl p-nitrobenzyl ammonium chloride into the reactor after the reaction is finished, heating to 65-75 ℃, continuously reacting for 4-6h, repeatedly washing for 3-5 times by using ethanol and isopropanol, and adjusting the product to be neutral by using hydrochloric acid to obtain modified chitosan; according to the method, carboxymethylation and quaternization treatment are carried out on chitosan, and positive and negative charge groups are introduced into a molecular chain of the chitosan at the same time, so that the water solubility of the chitosan can be improved, the chitosan can be more easily reacted with various substances, and the subsequent graphene oxide intercalation reaction can be promoted;
2) sequentially adding polyvinyl alcohol, modified chitosan, glacial acetic acid and glutaraldehyde into a nano titanium dioxide dispersion liquid, stirring for 30-40min in a water bath at 50-60 ℃, rotating at the speed of 150 plus 200r/min, drying a product for 5-8h at 60-70 ℃ after stirring to obtain a nano titanium dioxide/modified chitosan compound, adding graphene oxide into deionized water, mixing and stirring to obtain a graphene oxide dispersion liquid with the mass fraction of 0.2-0.5%, then adding the nano titanium dioxide/modified chitosan compound into the graphene oxide dispersion liquid, and performing ultrasonic treatment for 1-2h under 600 plus 800W ultrasonic wave to obtain the graphene oxide/nano titanium dioxide/modified chitosan compound; the nano titanium dioxide/modified chitosan compound is used for carrying out intercalation modification treatment on graphene oxide, epoxy groups on the surface of the graphene oxide are easy to break to form hydroxyl groups and amino groups, and can form intercalation compounding with carboxyl groups and hydroxyl groups in chitosan through hydrogen bonds, so that rough pores on the surface of the graphene oxide can be filled, a compound with a smooth surface is obtained, through the intercalation modification treatment, activation points on the graphene oxide can be activated and increased, the formation of hydrogen bond combination between the graphene oxide/nano titanium dioxide/modified chitosan compound and the surface of polymer microspheres can be promoted, and the adhesion of the compound on the surface of subsequent polymer microspheres can be promoted; preparing a compound by using nano titanium dioxide and modified chitosan, carrying out intercalation modification treatment on graphene oxide by using the compound, and filling and coating the surface of the graphene oxide, so that a white compound can be obtained, and the flexibility of the subsequently prepared microspheres can be further improved;
3) adding polylactic acid into a tetrahydrofuran solution, heating to 60-70 ℃, stirring and dissolving for 4-5h at the rotating speed of 80-150r/min to obtain a polylactic acid/tetrahydrofuran mixed solution, then adding dimethyl diallyl ammonium chloride, uniformly mixing, placing at-20 to-40 ℃ for low-temperature treatment for 2-3h, quickly placing a product into distilled water at 5-10 ℃ for extraction after treatment, replacing the distilled water every 4-5h for 3-4 times continuously, and vacuum drying the obtained product for 20-25h at 60-70 ℃ to obtain polylactic acid porous microspheres; the polylactic acid/tetrahydrofuran mixed solution is subjected to low-temperature treatment, the solution is subjected to liquid-liquid phase separation to form a polymer enrichment phase and a solvent enrichment phase, polylactic acid molecular chains with similar conformations in the polymer enrichment phase are arranged in an aggregation orientation manner to generate crystal nuclei, the crystal nuclei are diffused along the vicinity of the crystal nuclei, and crystals grow along the radial direction to form polylactic acid spherulites, so that polylactic acid porous microspheres can be obtained; the added dimethyl diallyl ammonium chloride enables the surface of the polylactic acid porous microsphere to contain quaternary ammonium salt groups, so that the polylactic acid porous microsphere has a certain charge amount, and the graphene oxide/nano titanium dioxide/modified chitosan compound is facilitated to form a coating layer on the surface of the polylactic acid porous microsphere under the electrostatic action;
4) adding polylactic acid porous microspheres into deionized water, treating for 30-50min under 300-400W ultrasonic waves, then adding graphene oxide/nano titanium dioxide/modified chitosan compound dispersion liquid, heating to 80-90 ℃, stirring for 20-25h at the rotation speed of 100-150r/min, cooling to room temperature, and obtaining the porous composite microspheres after centrifugal separation, washing and drying; heating and stirring the polylactic acid porous microspheres and the graphene oxide/nano titanium dioxide/modified chitosan compound dispersion liquid, and enabling the graphene oxide/nano titanium dioxide/modified chitosan compound to be coated on the surfaces of the polylactic acid porous microspheres under the electrostatic action and the hydrogen bond action, so that the flexibility and the strength of the porous microspheres can be enhanced;
5) mixing and stirring polyvinyl chloride and polypropylene, adding the filler, the porous composite microspheres, the antioxidant and the lubricant, stirring to obtain a mixture, putting the mixture into an extruder, and extruding and granulating to obtain the polymer plastic.
Preferably, the polymer plastic is used for processing plastic pencil leads, wherein in the preparation step 1), the mass ratio of the chitosan, the isopropanol, the sodium hydroxide solution, the chloroacetic acid and the triethyl-p-nitrobenzyl ammonium chloride is 1.2-1.7:18-23:1.8-2.1:1:1.7-2, the mass fraction of the sodium hydroxide solution is 35-40%, and the dosage of the first time and the second time is 2: 1; the mass fraction of the hydrochloric acid is 10-15%.
Preferably, the polymer plastic for processing the plastic pencil shaft is prepared by the following steps, wherein in the preparation step 2), the mass-to-volume ratio of the polyvinyl alcohol, the modified chitosan, the glacial acetic acid, the glutaraldehyde and the nano titanium dioxide dispersion is 1g: 0.2-0.4 g: 0.3-0.5 ml: 0.2-0.4 ml: 30-40 g; the mass ratio of the graphene oxide dispersion liquid to the nano titanium dioxide/modified chitosan compound is 90-120: 50-60.
Preferably, the polymer plastic is used for processing plastic pencil stems, wherein in the preparation step 3), the mass ratio of the polylactic acid to the tetrahydrofuran solution to the dimethyl diallyl ammonium chloride is 1:12-17: 0.02-0.05.
Preferably, the polymer plastic is used for processing a plastic pencil rod, wherein in the preparation step 4), the mass-to-volume ratio of the polylactic acid porous microspheres, the deionized water and the graphene oxide/modified chitosan composite dispersion liquid is 1g: 150-: 40-60ml, wherein the concentration of the graphene oxide/modified chitosan compound dispersion liquid is 1-3 mg/ml; the rotation speed of the centrifugal separation is 5000-; the drying temperature is 50-60 ℃, and the drying time is 10-15 h; the diameter of the porous composite microsphere is 50-80 um.
Preferably, the polymer plastic is used for processing plastic pencil stems, wherein in the preparation step 5), the raw materials comprise, by weight, 30-40% of polyvinyl chloride, 50-60% of polypropylene, 1-3% of a filler, 5-8% of porous composite microspheres, 0.2-0.5% of an antioxidant and 0.3-0.5% of a lubricant; the filler is one or more of calcium carbonate, titanium dioxide and talcum powder, the antioxidant is hindered phenol antioxidant, and the lubricant is one or more of calcium stearate and zinc stearate; the extrusion temperature of the extruder is 150-170 ℃, and the rotating speed of the extruder is 250-350 r/min; the particle size of the polymer plastic is 2-5 mm.
Compared with the prior art, the invention has the following advantages:
the polymer plastic prepared by the application utilizes the good toughening effect of the graphene oxide, a series of treatments are carried out on the graphene oxide, then the treated graphene oxide is coated on the surface of the polylactic acid porous microsphere, so as to obtain the white porous composite microsphere with the sealed and smooth surface, the composite microsphere is added into the conventional polymer plastic preparation raw material, on one hand, the density of the polymer plastic can be reduced, so that the interior of the polymer plastic is in a porous structure, so that the density of the polymer plastic can be reduced, on the other hand, because a large number of microspheres with smooth surfaces are distributed in the polymer plastic, when a blade is used for cutting the polymer plastic, and the blade is contacted with the composite microsphere in the polymer plastic, the smooth surface of the composite microsphere can reduce the frictional resistance between the blade and the composite microsphere, so that the polymer plastic is easy to cut, and because the microsphere has good flexibility, the blade can not cause the breakage of the microspheres during cutting, so that the integrity of the microspheres can be ensured; the polymer plastic is used for preparing the penholder of the plastic pencil, so that the curling resistance of the pencil can be effectively reduced, the pencil is easy to curl, the compact structure of a curling surface can be kept, the curling surface is not easy to be stained, and the neatness and the attractiveness of the plastic pencil are improved.
Detailed Description
The present invention will be further described with reference to specific embodiments.
Example 1
The polymer plastic for processing the plastic pencil shaft is prepared by the following specific steps:
1) sequentially adding chitosan, isopropanol, a sodium hydroxide solution and chloroacetic acid into a reactor, heating to 50 ℃, reacting for 8 hours, continuously adding the sodium hydroxide solution and triethyl-p-nitrobenzyl ammonium chloride into the reactor after the reaction is finished, heating to 65 ℃, continuously reacting for 6 hours, repeatedly washing for 3 times by using ethanol and isopropanol, and adjusting the product to be neutral by using hydrochloric acid to obtain the modified chitosan;
2) sequentially adding polyvinyl alcohol, modified chitosan, glacial acetic acid and glutaraldehyde into a nano titanium dioxide dispersion liquid, stirring for 40min in a water bath at 50 ℃, wherein the rotating speed is 150r/min, drying a product for 8h at 60 ℃ after stirring is finished to obtain a nano titanium dioxide/modified chitosan compound, adding graphene oxide into deionized water, mixing and stirring to obtain a graphene oxide dispersion liquid with the mass fraction of 0.2%, then adding the nano titanium dioxide/modified chitosan compound into the graphene oxide dispersion liquid, and performing ultrasonic treatment for 2h under 600W ultrasonic waves to obtain the graphene oxide/nano titanium dioxide/modified chitosan compound;
3) adding polylactic acid into a tetrahydrofuran solution, heating to 60 ℃, stirring and dissolving for 5 hours at the rotating speed of 80r/min to obtain a polylactic acid/tetrahydrofuran mixed solution, then adding dimethyl diallyl ammonium chloride, uniformly mixing, placing at-20 ℃ for low-temperature treatment for 3 hours, quickly placing a product into 5 ℃ distilled water for extraction after the treatment is finished, replacing the distilled water once every 4 hours, continuously replacing for 3 times, and performing vacuum drying on the obtained product for 25 hours at 60 ℃ to obtain polylactic acid porous microspheres;
4) adding polylactic acid porous microspheres into deionized water, treating for 50min under 300W ultrasonic waves, then adding graphene oxide/nano titanium dioxide/modified chitosan compound dispersion liquid, heating to 80 ℃, stirring for 25h at the rotating speed of 100r/min, cooling to room temperature, and obtaining the porous composite microspheres after centrifugal separation, washing and drying;
5) mixing and stirring polyvinyl chloride and polypropylene, adding the filler, the porous composite microspheres, the antioxidant and the lubricant, stirring to obtain a mixture, putting the mixture into an extruder, and extruding and granulating to obtain the polymer plastic.
Preferably, in the preparation step 1), the mass ratio of the chitosan, the isopropanol, the sodium hydroxide solution, the chloroacetic acid and the triethyl-p-nitrobenzyl ammonium chloride is 1.2:18:1.8:1:1.7, wherein the mass fraction of the sodium hydroxide solution is 35%, and the dosage of the first time and the second time is 2: 1; the mass fraction of the hydrochloric acid is 10%.
Preferably, in the preparation step 2), the mass ratio by volume of the polyvinyl alcohol, the modified chitosan, the glacial acetic acid, the glutaraldehyde and the nano titanium dioxide dispersion is 1g: 0.2 g: 0.3 ml: 0.2 ml: 30g of the total weight of the mixture; the mass ratio of the graphene oxide dispersion liquid to the nano titanium dioxide/modified chitosan compound is 90: 50.
Preferably, in the preparation step 3), the mass ratio of the polylactic acid to the tetrahydrofuran solution to the dimethyldiallylammonium chloride is 1:12: 0.02.
Preferably, in the preparation step 4), the mass-to-volume ratio of the polylactic acid porous microspheres to the deionized water to the graphene oxide/nano titanium dioxide/modified chitosan composite dispersion is 1g:150 ml: 40ml, wherein the concentration of the graphene oxide/modified chitosan compound dispersion liquid is 1 mg/ml; the rotation speed of the centrifugal separation is 5000r/min, and the centrifugal separation is carried out for 30 min; the drying temperature is 50 ℃, and the drying time is 15 h; the diameter of the porous composite microspheres is 50 um.
Preferably, in the preparation step 5), the raw materials comprise 30% of polyvinyl chloride, 60% of polypropylene, 3% of filler, 6.5% of porous composite microspheres, 0.2% of antioxidant and 0.3% of lubricant by weight; the filler is one or more of calcium carbonate, titanium dioxide and talcum powder, the antioxidant is hindered phenol antioxidant, and the lubricant is one or more of calcium stearate and zinc stearate; the extrusion temperature of the extruder is 150 ℃, and the rotating speed of the extruder is 250 r/min; the particle size of the polymer plastic is 2 mm.
Example 2
The polymer plastic for processing the plastic pencil shaft is prepared by the following specific steps:
1) sequentially adding chitosan, isopropanol, a sodium hydroxide solution and chloroacetic acid into a reactor, heating to 55 ℃, reacting for 7 hours, continuously adding the sodium hydroxide solution and triethyl-p-nitrobenzyl ammonium chloride into the reactor after the reaction is finished, heating to 70 ℃, continuously reacting for 5 hours, repeatedly washing for 4 times by using ethanol and isopropanol, and adjusting the product to be neutral by using hydrochloric acid to obtain the modified chitosan;
2) sequentially adding polyvinyl alcohol, modified chitosan, glacial acetic acid and glutaraldehyde into a nano titanium dioxide dispersion liquid, stirring for 35min in a water bath at 55 ℃, rotating at 180r/min, drying a product for 7h at 65 ℃ after stirring is finished to obtain a nano titanium dioxide/modified chitosan compound, adding graphene oxide into deionized water, mixing and stirring to obtain a graphene oxide dispersion liquid with the mass fraction of 0.4%, then adding the nano titanium dioxide/modified chitosan compound into the graphene oxide dispersion liquid, and performing ultrasonic treatment for 1.5h under 700W ultrasonic waves to obtain the graphene oxide/nano titanium dioxide/modified chitosan compound;
3) adding polylactic acid into a tetrahydrofuran solution, heating to 65 ℃, stirring and dissolving for 4.5 hours at the rotating speed of 120r/min to obtain a polylactic acid/tetrahydrofuran mixed solution, then adding dimethyl diallyl ammonium chloride, uniformly mixing, placing at-30 ℃ for low-temperature treatment for 2.5 hours, quickly placing a product into 8 ℃ distilled water for extraction after the treatment is finished, replacing the distilled water every 4.5 hours, continuously replacing for 3 times, and performing vacuum drying on the obtained product for 23 hours at 65 ℃ to obtain polylactic acid porous microspheres;
4) adding polylactic acid porous microspheres into deionized water, treating for 40min under 350W ultrasonic waves, then adding graphene oxide/nano titanium dioxide/modified chitosan compound dispersion liquid, heating to 85 ℃, stirring for 23h at the rotating speed of 130r/min, cooling to room temperature, and obtaining the porous composite microspheres after centrifugal separation, washing and drying;
5) mixing and stirring polyvinyl chloride and polypropylene, adding the filler, the porous composite microspheres, the antioxidant and the lubricant, stirring to obtain a mixture, putting the mixture into an extruder, and extruding and granulating to obtain the polymer plastic.
Preferably, in the preparation step 1), the mass ratio of the chitosan, the isopropanol, the sodium hydroxide solution, the chloroacetic acid and the triethyl-p-nitrobenzyl ammonium chloride is 1.5:20:1.9:1:1.8, wherein the mass fraction of the sodium hydroxide solution is 37%, and the dosage of the first time and the second time is 2: 1; the mass fraction of the hydrochloric acid is 13%.
Preferably, in the preparation step 2), the mass ratio by volume of the polyvinyl alcohol, the modified chitosan, the glacial acetic acid, the glutaraldehyde and the nano titanium dioxide dispersion is 1g: 0.3 g: 0.4 ml: 0.3 ml: 35g of a soybean milk powder; the mass ratio of the graphene oxide dispersion liquid to the nano titanium dioxide/modified chitosan compound is 105: 55.
Preferably, in the preparation step 3), the mass ratio of the polylactic acid to the tetrahydrofuran solution to the dimethyldiallylammonium chloride is 1:15: 0.03.
Preferably, in the preparation step 4), the mass-to-volume ratio of the polylactic acid porous microspheres to the deionized water to the graphene oxide/nano titanium dioxide/modified chitosan composite dispersion is 1g:180 ml: 50ml, wherein the concentration of the graphene oxide/modified chitosan compound dispersion liquid is 2 mg/ml; the rotation speed of the centrifugal separation is 7000r/min, and the centrifugal separation is carried out for 25 min; the drying temperature is 55 ℃, and the drying time is 13 h; the diameter of the porous composite microspheres is 70 um.
Preferably, in the preparation step 5), the raw materials comprise 35% of polyvinyl chloride, 55% of polypropylene, 1.3% of filler, 8% of porous composite microspheres, 0.3% of antioxidant and 0.4% of lubricant by weight; the filler is one or more of calcium carbonate, titanium dioxide and talcum powder, the antioxidant is hindered phenol antioxidant, and the lubricant is one or more of calcium stearate and zinc stearate; the extrusion temperature of the extruder is 160 ℃, and the rotating speed of the extruder is 300 r/min; the particle size of the polymer plastic is 3 mm.
Example 3
The polymer plastic for processing the plastic pencil shaft is prepared by the following specific steps:
1) sequentially adding chitosan, isopropanol, a sodium hydroxide solution and chloroacetic acid into a reactor, heating to 60 ℃, reacting for 6 hours, continuously adding the sodium hydroxide solution and triethyl-p-nitrobenzyl ammonium chloride into the reactor after the reaction is finished, heating to 75 ℃, continuously reacting for 4 hours, repeatedly washing for 5 times by using ethanol and isopropanol, and adjusting the product to be neutral by using hydrochloric acid to obtain modified chitosan;
2) sequentially adding polyvinyl alcohol, modified chitosan, glacial acetic acid and glutaraldehyde into a nano titanium dioxide dispersion liquid, stirring for 30min in a water bath at 60 ℃, wherein the rotating speed is 200r/min, drying a product for 5h at 70 ℃ after stirring is finished to obtain a nano titanium dioxide/modified chitosan compound, adding graphene oxide into deionized water, mixing and stirring to obtain a graphene oxide dispersion liquid with the mass fraction of 0.5%, then adding the nano titanium dioxide/modified chitosan compound into the graphene oxide dispersion liquid, and performing ultrasonic treatment for 1h under 800W ultrasonic wave to obtain the graphene oxide/nano titanium dioxide/modified chitosan compound;
3) adding polylactic acid into a tetrahydrofuran solution, heating to 70 ℃, stirring and dissolving for 4 hours at the rotating speed of 150r/min to obtain a polylactic acid/tetrahydrofuran mixed solution, then adding dimethyl diallyl ammonium chloride, uniformly mixing, placing into a low-temperature treatment system at-40 ℃ for 2 hours, quickly placing a product into distilled water at 10 ℃ for extraction after the treatment is finished, replacing the distilled water once every 5 hours, continuously replacing for 4 times, and drying the obtained product at 70 ℃ for 20 hours in vacuum to obtain polylactic acid porous microspheres;
4) adding polylactic acid porous microspheres into deionized water, treating for 30min under 400W ultrasonic waves, then adding graphene oxide/nano titanium dioxide/modified chitosan compound dispersion liquid, heating to 90 ℃, stirring for 20h at the rotating speed of 150r/min, cooling to room temperature, and obtaining the porous composite microspheres after centrifugal separation, washing and drying;
5) mixing and stirring polyvinyl chloride and polypropylene, adding the filler, the porous composite microspheres, the antioxidant and the lubricant, stirring to obtain a mixture, putting the mixture into an extruder, and extruding and granulating to obtain the polymer plastic.
Preferably, in the preparation step 1), the mass ratio of the chitosan, the isopropanol, the sodium hydroxide solution, the chloroacetic acid and the triethyl-p-nitrobenzyl ammonium chloride is 1.7:23:2.1:1:2, wherein the mass fraction of the sodium hydroxide solution is 40%, and the dosage of the first time and the second time is 2: 1; the mass fraction of the hydrochloric acid is 15%.
Preferably, in the preparation step 2), the mass ratio by volume of the polyvinyl alcohol, the modified chitosan, the glacial acetic acid, the glutaraldehyde and the nano titanium dioxide dispersion is 1g: 0.4 g: 0.5 ml: 0.4 ml: 40g of the total weight of the mixture; the mass ratio of the graphene oxide dispersion liquid to the nano titanium dioxide/modified chitosan compound is 120: 60.
Preferably, in the preparation step 3), the mass ratio of the polylactic acid to the tetrahydrofuran solution to the dimethyldiallylammonium chloride is 1:17: 0.05.
Preferably, in the preparation step 4), the mass-to-volume ratio of the polylactic acid porous microspheres to the deionized water to the graphene oxide/nano titanium dioxide/modified chitosan composite dispersion is 1g:200 ml: 60ml, wherein the concentration of the graphene oxide/modified chitosan compound dispersion liquid is 3 mg/ml; the rotating speed of the centrifugal separation is 8000r/min, and the centrifugation is carried out for 15 min; the drying temperature is 60 ℃, and the drying time is 10 hours; the diameter of the porous composite microspheres is 80 um.
Preferably, in the preparation step 5), the raw materials comprise 40% of polyvinyl chloride, 50% of polypropylene, 3% of filler, 6% of porous composite microspheres, 0.5% of antioxidant and 0.5% of lubricant by weight; the filler is one or more of calcium carbonate, titanium dioxide and talcum powder, the antioxidant is hindered phenol antioxidant, and the lubricant is one or more of calcium stearate and zinc stearate; the extrusion temperature of the extruder is 170 ℃, and the rotating speed of the extruder is 350 r/min; the particle size of the polymer plastic is 5 mm.
Comparative example 1: the chloroacetic acid in step 1) was removed and the process was the same as in example 1.
Comparative example 2: the triethyl-p-nitrobenzyl ammonium chloride in step 1) was removed and the process was the same as in example 1.
Comparative example 3: the nano titanium dioxide in the step 2) is removed, and the rest is the same as the embodiment 1.
Comparative example 4: dimethyl diallyl ammonium chloride in the step 3) is removed, and the rest is the same as the example 1.
Comparative example 5: the steps 1), 2) and 4) are removed, the porous polylactic acid microspheres prepared in the step 3) are used for replacing the porous composite microspheres in the step 5), and the rest is the same as the example 1.
Comparative example 6: removing the step 3), replacing the porous polylactic acid microspheres in the step 4) with solid polylactic acid microspheres with the same particle size and with quaternary ammonium salt groups on the surfaces, and the rest is the same as the embodiment 1.
Comparative example 7: the plastic pencil shaft material prepared in example 1 disclosed in publication No. CN108997677A was selected.
Comparative example 8: the plastic pencil shaft material was the same as comparative example 7 except that no foaming agent was included.
Test example: selecting a primary school in Fuyang city of Anhui province, preparing plastic pencils by using the polymer plastics provided in examples 1-3 and comparative examples 1-6 as plastic pencil holder raw materials, preparing the plastic pencils by using pencil holder materials provided in comparative examples 7-8 for a control group 1 and a control group 2, distributing 11 prepared plastic pencils to students of two to four years, 3 students of each year and 40 students in each class, allowing the students to curl the plastic pencils for a plurality of times (at least 15 times), recording feedback of difficulty of the students in curling the plastic pencils, distributing the curled pencils to the students for use, avoiding curling the plastic pencils in the using process, respectively recycling the plastic pencils after using for 2 days, and observing the cleanness of the curled surfaces of the plastic pencils, wherein the statistical results are as follows:
note: 1, the curling and cutting difficulty of the plastic pencil is divided into 5 grades, and the curling and cutting easiness is gradually reduced from 1 grade to 5 grades, wherein 1 grade is easiest, and 5 grades is most difficult;
2, the lead materials of all the plastic pencils are the same, and the components of other additives are completely the same except the types of polymer plastics in the material of the penholder;
and 3, dividing the curling grade of the plastic pencils in the test data according to the curling difficulty degree of each plastic pencil by students, taking the grade with the most obtained bills as the curling grade of the plastic pencils, counting the number of the two bills with the difference of more than 50 before obtaining the bills, and re-testing the bills if the number of the two bills is insufficient until the bills meet the regulations.
As can be seen from the above table, the plastic pencil rod prepared from the polymer plastic provided by the invention not only can reduce the coiling and cutting difficulty and enable the pencil rod to be easy to coil and cut, but also enables the coiling and cutting surface not to be easily stained, has high aesthetic degree and has wide application prospect.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention.
Claims (6)
1. The polymer plastic for processing the plastic pencil shaft is characterized by being prepared by the following specific steps:
1) sequentially adding chitosan, isopropanol, a sodium hydroxide solution and chloroacetic acid into a reactor, heating to 50-60 ℃, reacting for 6-8h, continuously adding the sodium hydroxide solution and triethyl p-nitrobenzyl ammonium chloride into the reactor after the reaction is finished, heating to 65-75 ℃, continuously reacting for 4-6h, repeatedly washing for 3-5 times by using ethanol and isopropanol, and adjusting the product to be neutral by using hydrochloric acid to obtain modified chitosan;
2) sequentially adding polyvinyl alcohol, modified chitosan, glacial acetic acid and glutaraldehyde into a nano titanium dioxide dispersion liquid, stirring for 30-40min in a water bath at 50-60 ℃, rotating at the speed of 150 plus 200r/min, drying a product for 5-8h at 60-70 ℃ after stirring to obtain a nano titanium dioxide/modified chitosan compound, adding graphene oxide into deionized water, mixing and stirring to obtain a graphene oxide dispersion liquid with the mass fraction of 0.2-0.5%, then adding the nano titanium dioxide/modified chitosan compound into the graphene oxide dispersion liquid, and performing ultrasonic treatment for 1-2h under 600 plus 800W ultrasonic wave to obtain the graphene oxide/nano titanium dioxide/modified chitosan compound;
3) adding polylactic acid into a tetrahydrofuran solution, heating to 60-70 ℃, stirring and dissolving for 4-5h at the rotating speed of 80-150r/min to obtain a polylactic acid/tetrahydrofuran mixed solution, then adding dimethyl diallyl ammonium chloride, uniformly mixing, placing at-20 to-40 ℃ for low-temperature treatment for 2-3h, quickly placing a product into distilled water at 5-10 ℃ for extraction after treatment, replacing the distilled water every 4-5h for 3-4 times continuously, and vacuum drying the obtained product for 20-25h at 60-70 ℃ to obtain polylactic acid porous microspheres;
4) adding polylactic acid porous microspheres into deionized water, treating for 30-50min under 300-400W ultrasonic waves, then adding graphene oxide/nano titanium dioxide/modified chitosan compound dispersion liquid, heating to 80-90 ℃, stirring for 20-25h at the rotation speed of 100-150r/min, cooling to room temperature, and obtaining the porous composite microspheres after centrifugal separation, washing and drying;
5) mixing and stirring polyvinyl chloride and polypropylene, adding the filler, the porous composite microspheres, the antioxidant and the lubricant, stirring to obtain a mixture, putting the mixture into an extruder, and extruding and granulating to obtain the polymer plastic.
2. The polymer plastic for processing plastic pencil shaft as claimed in claim 1, wherein in the preparation step 1), the mass ratio of the chitosan, the isopropanol, the sodium hydroxide solution, the chloroacetic acid and the triethyl-p-nitrobenzyl ammonium chloride is 1.2-1.7:18-23:1.8-2.1:1:1.7-2, wherein the mass fraction of the sodium hydroxide solution is 35-40%, and the first and second dosages are 2: 1; the mass fraction of the hydrochloric acid is 10-15%.
3. The polymer plastic for processing plastic pencil shaft as claimed in claim 1, wherein in the preparation step 2), the mass-to-volume ratio of the polyvinyl alcohol, the modified chitosan, the glacial acetic acid, the glutaraldehyde and the nano titanium dioxide dispersion is 1g: 0.2-0.4 g: 0.3-0.5 ml: 0.2-0.4 ml: 30-40 g; the mass ratio of the graphene oxide dispersion liquid to the nano titanium dioxide/modified chitosan compound is 90-120: 50-60.
4. The polymer plastic for processing a plastic pencil shaft as claimed in claim 1, wherein in the preparation step 3), the mass ratio of the polylactic acid, the tetrahydrofuran solution and the dimethyldiallylammonium chloride is 1:12-17: 0.02-0.05.
5. The polymer plastic for processing the plastic pencil shaft as claimed in claim 1, wherein in the preparation step 4), the mass-to-volume ratio of the polylactic acid porous microspheres, the deionized water and the graphene oxide/nano titanium dioxide/modified chitosan composite dispersion is 1g: 150-: 40-60ml, wherein the concentration of the graphene oxide/modified chitosan compound dispersion liquid is 1-3 mg/ml; the rotation speed of the centrifugal separation is 5000-; the drying temperature is 50-60 ℃, and the drying time is 10-15 h; the diameter of the porous composite microsphere is 50-80 um.
6. The polymer plastic for processing plastic pencil leads as claimed in claim 1, wherein in the preparation step 5), the raw materials comprise, by weight, 30-40% of polyvinyl chloride, 50-60% of polypropylene, 1-3% of a filler, 5-8% of porous composite microspheres, 0.2-0.5% of an antioxidant and 0.3-0.5% of a lubricant; the filler is one or more of calcium carbonate, titanium dioxide and talcum powder, the antioxidant is hindered phenol antioxidant, and the lubricant is one or more of calcium stearate and zinc stearate; the extrusion temperature of the extruder is 150-170 ℃, and the rotating speed of the extruder is 250-350 r/min; the particle size of the polymer plastic is 2-5 mm.
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| CN201910973169.8A CN110791013A (en) | 2019-10-14 | 2019-10-14 | Polymer plastic for processing plastic pencil holder |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910973169.8A CN110791013A (en) | 2019-10-14 | 2019-10-14 | Polymer plastic for processing plastic pencil holder |
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| CN110791013A true CN110791013A (en) | 2020-02-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158006A (en) * | 2020-10-10 | 2021-01-01 | 浙江彭胜文教用品股份有限公司 | Plastic pencil and production process thereof |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158006A (en) * | 2020-10-10 | 2021-01-01 | 浙江彭胜文教用品股份有限公司 | Plastic pencil and production process thereof |
| CN112158006B (en) * | 2020-10-10 | 2022-01-11 | 浙江彭胜文教用品股份有限公司 | Plastic pencil and production process thereof |
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