CN111548548A - Special modified cellulose toughened HDPE material for plastic chairs and preparation thereof - Google Patents

Special modified cellulose toughened HDPE material for plastic chairs and preparation thereof Download PDF

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CN111548548A
CN111548548A CN202010531890.4A CN202010531890A CN111548548A CN 111548548 A CN111548548 A CN 111548548A CN 202010531890 A CN202010531890 A CN 202010531890A CN 111548548 A CN111548548 A CN 111548548A
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modified cellulose
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polyethylene
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CN111548548B (en
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胡森川
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ZHEJIANG SENCHUAN FURNITURE CO Ltd
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ZHEJIANG SENCHUAN FURNITURE CO Ltd
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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Abstract

The invention discloses a modified cellulose toughened HDPE plastic chair special material which comprises, by weight, 50-80 parts of high-density polyethylene, 5-15 parts of waste polyethylene, 10-20 parts of modified cellulose, 3-6 parts of carbon fiber, 2-5 parts of glass fiber, 30-50 parts of combined filler, 0.5-1.5 parts of poly α -methyl styrene, 1-3 parts of antioxidant, 1-2 parts of dispersing agent, 1-2 parts of coupling agent and 1-2 parts of lubricating agent, wherein the modified cellulose is prepared from the following raw materials of carboxymethyl cellulose, polylactic acid, flaky alumina, polyamide elastomer, diphenylmethane diisocyanate and dibutyltin dilaurate, and the density of the high-density polyethylene is 0.91-0.94g/cm3The melt flow mass rate is 8-8.6g/10 min. The invention discloses a preparation method of the modified cellulose toughened HDPE material special for plastic chairs.

Description

Special modified cellulose toughened HDPE material for plastic chairs and preparation thereof
Technical Field
The invention relates to the technical field of plastic chairs, in particular to a special material for a modified cellulose toughened HDPE plastic chair and a preparation method thereof.
Background
The thermoplastic plastic product has the advantages of low density and low linear expansion coefficient, can reduce the shrinkage rate in the product forming process and the like, greatly expands the use of plastics in daily life, and gradually replaces metal and wood. In the current daily life, the seat is generally made of thermoplastic plastics, so that the attractiveness and the design flexibility of the seat are greatly improved, and the processing, transferring and maintaining cost is reduced, which is the necessity for the development of the seat towards light weight, energy conservation, attractiveness, safety and environmental protection.
Seat processing plastics are required to have excellent aging resistance, wear resistance and impact resistance, and currently, the most used amount of general-purpose modified plastics such as PP, PE, PVC, HDPE and the like are used. High Density Polyethylene (HDPE) is a non-polar thermoplastic resin with high crystallinity, the appearance of the original HDPE is milk white, the original HDPE is semi-transparent to a certain degree at a micro-thin section, and the HDPE has good heat resistance and cold resistance, good chemical stability, higher rigidity, good mechanical strength, good dielectric property and good environmental stress cracking resistance.
However, the existing plastic seat has the disadvantages of poor toughness, weak impact resistance, easy damage and fracture, scratch generation, aesthetic influence and short service life due to unreasonable raw material proportion during processing, and the performance of the existing plastic seat can not meet the requirements gradually, so that novel modified plastics need to be developed.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a special material for a modified cellulose toughened HDPE plastic chair and a preparation method thereof.
A modified cellulose toughened HDPE material special for plastic chairs comprises the following raw materials in parts by weight: 50-80 parts of high-density polyethylene, 5-15 parts of waste polyethylene, 10-20 parts of modified cellulose, 3-6 parts of carbon fiber, 2-5 parts of glass fiber, 30-50 parts of combined filler, 0.5-1.5 parts of poly-alpha-methyl styrene, 1-3 parts of antioxidant, 1-2 parts of dispersant, 1-2 parts of coupling agent and 1-2 parts of lubricant;
the modified cellulose is prepared from the following raw materials: carboxymethyl cellulose, polylactic acid, flaky alumina, polyamide elastomer, diphenylmethane diisocyanate and dibutyltin dilaurate.
Preferably, the high density polyethylene has a density of 0.91 to 0.94g/cm3The melt flow mass rate (MFR) was 8 to 8.6g/10min (test conditions: 190 ℃/2.16 kg).
Preferably, the combined filler is at least two of talcum powder, aluminum borate whisker, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber and quartz sand.
Preferably, the coupling agent is a silane coupling agent, preferably gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-methacryloxypropyltrimethoxysilane.
Preferably, the lubricant is at least one of polyethylene wax, polypropylene wax, low molecular lipid lubricant, metal soap lubricant, stearic acid complex lipid lubricant, and amide lubricant.
Preferably, the antioxidant is at least one of phenol antioxidant, amine antioxidant, phosphite antioxidant and semi-hindered phenol antioxidant, preferably at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, N-N' -hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide) and tris (2, 4-di-tert-butylphenyl) phosphite
Preferably, in the raw materials of the modified cellulose, the mass ratio of carboxymethyl cellulose, polylactic acid, flaky alumina, polyamide elastomer, diphenylmethane diisocyanate and dibutyltin dilaurate is 5-10: 20-30: 3-8: 1-4: 1-3: 0.1-0.18.
Preferably, the modified cellulose is prepared by the following process: dissolving carboxymethyl cellulose in acetone, adjusting the temperature to 60-80 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate to react for 40-50min under the stirring state, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding polylactic acid, flaky alumina and polyamide elastomer, heating to 190 ℃ at the temperature of 150 ℃, melting and stirring for 4-10min, cooling, and crushing to obtain the modified cellulose.
The preparation method of the special modified cellulose toughened HDPE material for the plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, combined filler and poly alpha-methyl styrene, adding an antioxidant, a dispersing agent, a coupling agent and a lubricating agent, and continuously stirring to obtain a premix;
and (3) mixing the premix for 3-5min at the mixing temperature of 120-128 ℃, then performing melt extrusion and granulation to obtain the modified cellulose toughened HDPE material special for the plastic chair.
Preferably, a double-screw extruder is adopted for melt extrusion, wherein the temperature of a first area of the double-screw extruder is 150-.
The technical effects of the invention are as follows:
in the modified cellulose, the diphenylmethane diisocyanate is grafted on the surface of the carboxymethyl cellulose, so that the compatibility with the polylactic acid containing a carbonyl structure is good, extremely strong intermolecular force is generated, the toughening effect is obvious, but microcracks are easily generated on the surface of the carboxymethyl cellulose, the polyamide elastomer is further introduced into the modified cellulose, the flaky alumina can promote the high dispersion between the polyamide elastomer and the grafted cellulose, can reduce the microcrack phenomenon caused by thermal expansion, reduces the size of stress concentration and microcracks, needs to absorb a large amount of external energy before fracture, and has an obvious synergistic toughening effect.
The modified cellulose is used as the toughening agent, the toughening agent has good compatibility with high-density polyethylene and waste polyethylene, can generate a mutual cross-linking phenomenon with molecular chains of the high-density polyethylene and the waste polyethylene, has an efficient plasticizing effect, greatly improves the toughness of the material, can promote bridging action among materials by matching with carbon fibers and glass fibers, and forms uniform dispersion phases in polymer macromolecules by arranging the modified cellulose, the carbon fibers and the glass fibers, so that the impact resistance of a system is greatly improved, and the phenomenon of product fracture is avoided; the modified cellulose is adopted to replace a common plastic toughening agent, and multiple tests prove that the special material for the plastic chair has higher toughness and impact strength and long service life.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A special material for a plastic chair made of modified cellulose toughened HDPE comprises the following raw materials: 50kg of high-density polyethylene, 15kg of waste polyethylene, 10kg of modified cellulose, 6kg of carbon fiber, 2kg of glass fiber, 40kg of talcum powder, 10kg of aluminum borate whisker, 0.5kg of poly-alpha-methyl styrene, 3kg of 2-tert-butyl-4-methyl phenol, 1kg of dispersing agent, 2kg of gamma-aminopropyltriethoxysilane and 1kg of sodium stearate.
The high density polyethylene has a density of 0.91g/cm3The melt flow mass rate was 8.57g/10min (test conditions: 190 ℃/2.16 kg). The modified cellulose is prepared by the following process: dissolving 10kg of carboxymethyl cellulose in 40kg of acetone, adjusting the temperature to 80 ℃, adding 1kg of diphenylmethane diisocyanate and 0.18kg of dibutyltin dilaurate under a stirring state to react for 40min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 30kg of polylactic acid, 3kg of flaky alumina and 4kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 10min at the temperature of 150 ℃, wherein the stirring speed is 150r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special modified cellulose toughened HDPE material for the plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, talcum powder, aluminum borate whisker and poly-alpha-methylstyrene, then adding 2-tert-butyl-4-methylphenol, a dispersing agent, gamma-aminopropyltriethoxysilane and sodium stearate, and continuously stirring to obtain a premix;
and (2) mixing the premix for 5min at the mixing temperature of 120 ℃, then carrying out melt extrusion by adopting a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 155 ℃, the temperature of a second zone of the double-screw extruder is 161 ℃, the temperature of a third zone of the double-screw extruder is 175 ℃, the temperature of a fourth zone of the double-screw extruder is 190 ℃, the temperature of a machine head is 188 ℃, the residence time is 50s, the pressure is 6.5MPa, and the screw rotation speed is 200r/min, and.
Example 2
A special material for a plastic chair made of modified cellulose toughened HDPE comprises the following raw materials: 80kg of high-density polyethylene, 5kg of waste polyethylene, 20kg of modified cellulose, 3kg of carbon fiber, 5kg of glass fiber, 5kg of polyborate short fiber, 25kg of titanium dioxide, 1.5kg of poly-alpha-methyl styrene, 1kg of N-isopropyl-N' -phenyl p-phenylenediamine, 2kg of dispersing agent, 1kg of gamma-aminopropyltriethoxysilane and 2kg of oleamide.
The density of the high density polyethylene is 0.94g/cm3The melt flow mass rate was 8.03g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 5kg of carboxymethyl cellulose in 80kg of acetone, adjusting the temperature to 60 ℃, adding 3kg of diphenylmethane diisocyanate and 0.1kg of dibutyltin dilaurate under stirring to react for 50min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 20kg of polylactic acid, 8kg of flaky alumina and 1kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 4min at 190 ℃, wherein the stirring speed is 200r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special modified cellulose toughened HDPE material for the plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, polyborate short fiber, titanium dioxide and poly-alpha-methylstyrene, then adding N-isopropyl-N' -phenyl-p-phenylenediamine, a dispersing agent, gamma-aminopropyltriethoxysilane and oleamide, and continuously stirring to obtain a premix;
and (2) mixing the premix for 3min at the mixing temperature of 128 ℃, then carrying out melt extrusion by adopting a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 150 ℃, the temperature of a second zone is 166 ℃, the temperature of a third zone is 170 ℃, the temperature of a fourth zone is 210 ℃, the temperature of a machine head is 182 ℃, the residence time is 80s, the pressure is 4.5MPa, and the screw rotation speed is 250r/min, and granulating to obtain the special material for the modified cellulose toughened HDPE plastic chair.
Example 3
A special material for a plastic chair made of modified cellulose toughened HDPE comprises the following raw materials: 60kg of high-density polyethylene, 12kg of waste polyethylene, 12kg of modified cellulose, 5kg of carbon fiber, 3kg of glass fiber, 25kg of medical stone, 20kg of polypropylene fiber, 0.8kg of poly-alpha-methyl styrene, 2.5kg of bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 1.3kg of dispersing agent, 1.8kg of gamma-aminopropylmethyldiethoxysilane and 1.3kg of stearic acid amide.
The density of the high density polyethylene is 0.92g/cm3The melt flow mass rate was 8.40g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 8kg of carboxymethyl cellulose in 50kg of acetone, adjusting the temperature to 75 ℃, adding 1.5kg of diphenylmethane diisocyanate and 0.16kg of dibutyltin dilaurate under stirring for reacting for 40min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 27kg of polylactic acid, 4kg of flaky alumina and 3kg of polyamide elastomer, conveying into a high-speed mixer, melting and stirring for 8min at 160 ℃, wherein the stirring speed is 160r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special modified cellulose toughened HDPE material for the plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, medical stone, polypropylene fiber and poly-alpha-methylstyrene, then adding bis (3, 5-di-tert-butyl-4-hydroxybenzyl) thioether, a dispersing agent, gamma-aminopropyl methyl diethoxy silane and stearic acid amide, and continuously stirring to obtain a premix;
and (2) mixing the premix for 4.5min at the mixing temperature of 122 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the first-zone temperature of the double-screw extruder is 154 ℃, the second-zone temperature is 162 ℃, the third-zone temperature is 174 ℃, the fourth-zone temperature is 195 ℃, the head temperature is 186 ℃, the residence time is 60s, the pressure is 6MPa, the screw rotation speed is 220r/min, and the special material for the modified cellulose toughened HDPE plastic chair is obtained by granulation.
Example 4
A special material for a plastic chair made of modified cellulose toughened HDPE comprises the following raw materials: 70kg of high-density polyethylene, 8kg of waste polyethylene, 18kg of modified cellulose, 4kg of carbon fiber, 4kg of glass fiber, 15kg of talcum powder, 15kg of quartz sand, 5kg of aluminum borate whisker, 1.2kg of poly-alpha-methyl styrene, 1.5kg of N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine, 1.7kg of dispersing agent, 1.2kg of gamma-methacryloxypropyl trimethoxysilane and 1.7kg of stearic acid monoglyceride.
The density of the high density polyethylene is 0.93g/cm3The melt flow mass rate was 8.24g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 6kg of carboxymethyl cellulose in 70kg of acetone, adjusting the temperature to 65 ℃, adding 2.5kg of diphenylmethane diisocyanate and 0.12kg of dibutyltin dilaurate under stirring for reacting for 50min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 23kg of polylactic acid, 7kg of flaky alumina and 2kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 6min at 180 ℃, wherein the stirring speed is 180r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special modified cellulose toughened HDPE material for the plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, talcum powder, quartz sand, aluminum borate whisker and poly-alpha-methylstyrene, then adding N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine, a dispersing agent, gamma-methacryloxypropyl trimethoxysilane and glycerol monostearate, and continuously stirring to obtain a premix;
and (3) mixing the premix for 3.5min at the mixing temperature of 126 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the first-zone temperature of the double-screw extruder is 152 ℃, the second-zone temperature is 165 ℃, the third-zone temperature is 171 ℃, the fourth-zone temperature is 205 ℃, the head is 184 ℃, the residence time is 70s, the pressure is 5MPa, and the screw rotation speed is 240r/min, and granulating to obtain the special material for the modified cellulose toughened HDPE plastic chair.
Example 5
A special material for a plastic chair made of modified cellulose toughened HDPE comprises the following raw materials: 65kg of high-density polyethylene, 10kg of waste polyethylene, 15kg of modified cellulose, 4.5kg of carbon fiber, 3.5kg of glass fiber, 5kg of polyborate short fiber, 10kg of titanium dioxide, 10kg of medical stone, 15kg of polypropylene fiber, 1kg of poly-alpha-methylstyrene, 2kg of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.5kg of dispersing agent, 1.5kg of gamma-methacryloxypropyl trimethoxy silane and 1.5kg of polyethylene wax.
The density of the high density polyethylene is 0.925g/cm3The melt flow mass rate was 8.36g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 7kg of carboxymethyl cellulose in 60kg of acetone, adjusting the temperature to 70 ℃, adding 2kg of diphenylmethane diisocyanate and 0.14kg of dibutyltin dilaurate under stirring to react for 45min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 25kg of polylactic acid, 5.5kg of flaky alumina and 2.5kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 7min at the temperature of 170 ℃, wherein the stirring speed is 170r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special modified cellulose toughened HDPE material for the plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber and poly-alpha-methylstyrene, and then adding tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, a dispersing agent, gamma-methacryloxypropyl trimethoxysilane and polyethylene wax to continuously stir to obtain a premix;
and (2) mixing the premix for 4min at the mixing temperature of 124 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 153 ℃, the temperature of a second zone of the double-screw extruder is 164 ℃, the temperature of a third zone of the double-screw extruder is 173 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head is 185 ℃, the residence time is 65s, the pressure is 5.5MPa, and the screw rotation speed is 230r/min, and.
Comparative example 1
The HDPE plastic chair special material comprises the following raw materials: 65kg of high-density polyethylene, 10kg of waste polyethylene, 15kg of carboxymethyl cellulose, 4.5kg of carbon fiber, 3.5kg of glass fiber, 5kg of polyborate short fiber, 10kg of titanium dioxide, 10kg of medical stone, 15kg of polypropylene fiber, 1kg of poly-alpha-methyl styrene, 2kg of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.5kg of dispersing agent, 1.5kg of gamma-methacryloxypropyl trimethoxy silane and 1.5kg of polyethylene wax.
The density of the high density polyethylene is 0.925g/cm3The melt flow mass rate was 8.36g/10min (test conditions: 190 ℃ C./2.16 kg).
The preparation method of the special material for the HDPE plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, carboxymethyl cellulose, carbon fiber, glass fiber, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber and poly alpha-methylstyrene, and then adding tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, a dispersing agent, gamma-methacryloxypropyl trimethoxysilane and polyethylene wax to continuously stir to obtain a premix;
and (3) mixing the premix for 4min at the mixing temperature of 124 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 153 ℃, the temperature of a second zone of the double-screw extruder is 164 ℃, the temperature of a third zone of the double-screw extruder is 173 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head is 185 ℃, the residence time is 65s, the pressure is 5.5MPa, and the screw rotation speed is 230.
Comparative example 2
The HDPE plastic chair special material comprises the following raw materials: 65kg of high-density polyethylene, 10kg of waste polyethylene, 15kg of modified cellulose, 8kg of carboxymethyl cellulose, 5kg of polyborate short fiber, 10kg of titanium dioxide, 10kg of medical stone, 15kg of polypropylene fiber, 1kg of poly-alpha-methyl styrene, 2kg of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.5kg of dispersing agent, 1.5kg of gamma-methacryloxypropyl trimethoxy silane and 1.5kg of polyethylene wax.
The density of the high density polyethylene is 0.925g/cm3The melt flow mass rate was 8.36g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 7kg of carboxymethyl cellulose in 60kg of acetone, adjusting the temperature to 70 ℃, adding 2kg of diphenylmethane diisocyanate and 0.14kg of dibutyltin dilaurate under stirring to react for 45min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 25kg of polylactic acid, 5.5kg of flaky alumina and 2.5kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 7min at the temperature of 170 ℃, wherein the stirring speed is 170r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special material for the HDPE plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carboxymethyl cellulose, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber and poly-alpha-methylstyrene, and then adding tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, a dispersing agent, gamma-methacryloxypropyl trimethoxysilane and polyethylene wax to continuously stir to obtain a premix;
and (3) mixing the premix for 4min at the mixing temperature of 124 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 153 ℃, the temperature of a second zone of the double-screw extruder is 164 ℃, the temperature of a third zone of the double-screw extruder is 173 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head is 185 ℃, the residence time is 65s, the pressure is 5.5MPa, and the screw rotation speed is 230.
Comparative example 3
The HDPE plastic chair special material comprises the following raw materials: 65kg of high-density polyethylene, 10kg of waste polyethylene, 15kg of modified cellulose, 4.5kg of carbon fiber, 3.5kg of glass fiber, 5kg of polyborate short fiber, 10kg of titanium dioxide, 10kg of medical stone, 15kg of polypropylene fiber, 1kg of poly-alpha-methylstyrene, 2kg of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.5kg of dispersing agent, 1.5kg of gamma-methacryloxypropyl trimethoxy silane and 1.5kg of polyethylene wax.
The density of the high density polyethylene is 0.925g/cm3The melt flow mass rate was 8.36g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 7kg of carboxymethyl cellulose in 60kg of acetone, adjusting the temperature to 70 ℃, adding 2kg of diphenylmethane diisocyanate and 0.14kg of dibutyltin dilaurate under stirring for reacting for 45min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 5.5kg of flaky alumina and 2.5kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 7min at the temperature of 170 ℃, wherein the stirring speed is 170r/min, cooling and crushing to obtain the modified cellulose.
The preparation method of the special material for the HDPE plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber and poly-alpha-methylstyrene, and then adding tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, a dispersing agent, gamma-methacryloxypropyl trimethoxysilane and polyethylene wax to continuously stir to obtain a premix;
and (3) mixing the premix for 4min at the mixing temperature of 124 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 153 ℃, the temperature of a second zone of the double-screw extruder is 164 ℃, the temperature of a third zone of the double-screw extruder is 173 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head is 185 ℃, the residence time is 65s, the pressure is 5.5MPa, and the screw rotation speed is 230.
Comparative example 4
The HDPE plastic chair special material comprises the following raw materials: 65kg of high-density polyethylene, 10kg of waste polyethylene, 15kg of modified cellulose, 4.5kg of carbon fiber, 3.5kg of glass fiber, 5kg of polyborate short fiber, 10kg of titanium dioxide, 10kg of medical stone, 15kg of polypropylene fiber, 1kg of poly-alpha-methylstyrene, 2kg of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1.5kg of dispersing agent, 1.5kg of gamma-methacryloxypropyl trimethoxy silane and 1.5kg of polyethylene wax.
The density of the high density polyethylene is 0.925g/cm3The melt flow mass rate was 8.36g/10min (test conditions: 190 ℃ C./2.16 kg). The modified cellulose is prepared by the following process: dissolving 7kg of carboxymethyl cellulose in 60kg of acetone, adjusting the temperature to 70 ℃, adding 2kg of diphenylmethane diisocyanate and 0.14kg of dibutyltin dilaurate under a stirring state to react for 45min, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding 25kg of polylactic acid and 2.5kg of polyamide elastomer, feeding into a high-speed mixer, melting and stirring for 7min at the temperature of 170 ℃, wherein the stirring speed is 170r/min, cooling, and crushing to obtain the modified cellulose.
The preparation method of the special material for the HDPE plastic chair comprises the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber and poly-alpha-methylstyrene, and then adding tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, a dispersing agent, gamma-methacryloxypropyl trimethoxysilane and polyethylene wax to continuously stir to obtain a premix;
and (3) mixing the premix for 4min at the mixing temperature of 124 ℃, then carrying out melt extrusion by using a double-screw extruder, wherein the temperature of a first zone of the double-screw extruder is 153 ℃, the temperature of a second zone of the double-screw extruder is 164 ℃, the temperature of a third zone of the double-screw extruder is 173 ℃, the temperature of a fourth zone of the double-screw extruder is 200 ℃, the temperature of a machine head is 185 ℃, the residence time is 65s, the pressure is 5.5MPa, and the screw rotation speed is 230.
The special modified cellulose toughened HDPE plastic chair material obtained in example 5 and the special HDPE plastic chair material obtained in comparative examples 1-4 are dried in a blast oven at 70-80 ℃ for 4-6h, then injection molded on an 80T injection molding machine to prepare samples, and then performance tests are carried out, wherein the results are as follows:
Figure BDA0002535603830000141
wherein the tensile strength and elongation at break are measured according to ASTM D638, the impact strength is measured according to ASTM D256, the heat distortion temperature is measured according to ASTM D648, and the thermal conductivity is measured according to GB/T2256.
From the above results, it can be seen that: the modified cellulose is used as the toughening agent, the toughening agent has good compatibility with high-density polyethylene and waste polyethylene, the toughness of the material is greatly improved, the bridging effect between materials can be promoted by matching with the carbon fiber and the glass fiber, the modified cellulose, the carbon fiber and the glass fiber are arranged in polymer macromolecules to form uniform dispersion phases, the impact resistance of a system is greatly improved, and the phenomenon of product fracture is avoided.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The material special for the modified cellulose toughened HDPE plastic chair is characterized by comprising the following raw materials in parts by weight: 50-80 parts of high-density polyethylene, 5-15 parts of waste polyethylene, 10-20 parts of modified cellulose, 3-6 parts of carbon fiber, 2-5 parts of glass fiber, 30-50 parts of combined filler, 0.5-1.5 parts of poly-alpha-methyl styrene, 1-3 parts of antioxidant, 1-2 parts of dispersant, 1-2 parts of coupling agent and 1-2 parts of lubricant;
the modified cellulose is prepared from the following raw materials: carboxymethyl cellulose, polylactic acid, flaky alumina, polyamide elastomer, diphenylmethane diisocyanate and dibutyltin dilaurate.
2. The material as claimed in claim 1, wherein the density of the high density polyethylene is 0.91-0.94g/cm3The melt flow mass rate is 8-8.6g/10 min.
3. The material as claimed in claim 1, wherein the combined filler is at least two of talc powder, aluminum borate whisker, polyborate short fiber, titanium dioxide, medical stone, polypropylene fiber, and quartz sand.
4. The material as claimed in claim 1, wherein the coupling agent is silane coupling agent, preferably γ -aminopropyltriethoxysilane, γ -aminopropylmethyldiethoxysilane, and γ -methacryloxypropyltrimethoxysilane.
5. The material as claimed in claim 1, wherein the lubricant is at least one of polyethylene wax, polypropylene wax, low molecular weight lipid lubricant, metal soap lubricant, stearic acid complex lipid lubricant, and amide lubricant.
6. The material as claimed in claim 1, wherein the antioxidant is at least one of phenolic antioxidant, amine antioxidant, phosphite antioxidant, and semi-hindered phenolic antioxidant.
7. The material special for the modified cellulose toughened HDPE plastic chair as claimed in claim 1, wherein the raw materials of the modified cellulose comprise carboxymethyl cellulose, polylactic acid, flaky alumina, polyamide elastomer, diphenylmethane diisocyanate and dibutyltin dilaurate in a mass ratio of 5-10: 20-30: 3-8: 1-4: 1-3: 0.1-0.18.
8. The material special for the modified cellulose toughened HDPE plastic chair as claimed in any one of claims 1 to 7, wherein the modified cellulose is prepared by the following process: dissolving carboxymethyl cellulose in acetone, adjusting the temperature to 60-80 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate to react for 40-50min under the stirring state, cooling, precipitating by using isoamyl alcohol, washing by using toluene, drying, adding polylactic acid, flaky alumina and polyamide elastomer, heating to 190 ℃ at the temperature of 150 ℃, melting and stirring for 4-10min, cooling, and crushing to obtain the modified cellulose.
9. The preparation method of the modified cellulose toughened HDPE plastic chair special material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
uniformly stirring high-density polyethylene, waste polyethylene, modified cellulose, carbon fiber, glass fiber, combined filler and poly alpha-methyl styrene, adding an antioxidant, a dispersing agent, a coupling agent and a lubricating agent, and continuously stirring to obtain a premix;
and (3) mixing the premix for 3-5min at the mixing temperature of 120-128 ℃, then performing melt extrusion and granulation to obtain the modified cellulose toughened HDPE material special for the plastic chair.
10. The method for preparing the special material for the modified cellulose toughened HDPE plastic chair as claimed in claim 9, wherein the melt extrusion is carried out by a double-screw extruder, the temperature of the first zone of the double-screw extruder is 150-.
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CN101831801A (en) * 2010-05-07 2010-09-15 黄山华芮科技有限公司 Durable cellulose fiber and application thereof
CN102977460A (en) * 2012-12-12 2013-03-20 奇瑞汽车股份有限公司 Injecting molding grade natural fiber composite material and preparation method thereof

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CN107011640B (en) * 2017-04-10 2019-06-28 上海应用技术大学 A kind of cellulose toughening modified polylactic acid composite material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831801A (en) * 2010-05-07 2010-09-15 黄山华芮科技有限公司 Durable cellulose fiber and application thereof
CN102977460A (en) * 2012-12-12 2013-03-20 奇瑞汽车股份有限公司 Injecting molding grade natural fiber composite material and preparation method thereof

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