CN108641206A - Recoverying and utilizing method, poly styrene composite material and the application of waste electric products shell polystyrene plastics - Google Patents
Recoverying and utilizing method, poly styrene composite material and the application of waste electric products shell polystyrene plastics Download PDFInfo
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- CN108641206A CN108641206A CN201810238755.3A CN201810238755A CN108641206A CN 108641206 A CN108641206 A CN 108641206A CN 201810238755 A CN201810238755 A CN 201810238755A CN 108641206 A CN108641206 A CN 108641206A
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/03—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
Abstract
The invention discloses a kind of recoverying and utilizing method, poly styrene composite material and the applications of waste electric products shell polystyrene plastics, are related to plastics recovery technical field.This method includes regenerating 50 70 parts of polystyrene after particle and 25 parts of discarded cloth waste, the magnesium borate crystal whisker of 5 10 parts of activation, the carbon nanotube of 10 20 parts of activation, 3 15 parts of acicular wollastonite, 12 parts of compatilizer, 12 parts of toughener and 0.5 1 parts of mix lubricant through melt blending and cooling granulation, obtains poly styrene composite material；The magnesium borate crystal whisker of activation is that whisker obtains after the processing of TritonX 100, and the carbon nanotube of activation is that carbon nanotube obtains after cyclodextrin and ionic liquid processing.The HIPS composite of high-dimensional stability, high-fire resistance and creep resistant can be made in polystyrene plastics after the method for the present invention recycles, and can be reused in manufacture large scale product product.
Description
Technical field
The present invention relates to plastics recovery technical fields, in particular to a kind of waste electric products shell polystyrene
Recoverying and utilizing method, poly styrene composite material and the application of plastics.
Background technology
With the development of plastic industry and being on the increase for plastic product, a large amount of waste plastic all is being generated daily, no
Environment is only polluted, the wasting of resources is also brought, thus the recovery processing of waste recycles the heat for becoming global modifying plastics industry
Point and eager problem to be solved.It being shown according to statistics, China cities and towns electronic product scraps total amount and is expected to be up to 1,300,000,000,
With every computer 3 kilograms are used using 5 kilograms of plastics, air-conditioning using 3 kilograms of plastics, television set using 4 kilograms of plastics, refrigerator
Plastics, mobile phone are calculated using 100g plastics, i.e., the waste plastic of generation are up to 500,000 by the electric equipment products scrapped every year
Ton or more, and 50% use HIPS (high impact in the plastics used in these electric equipment products
Polystyrene, impact resistance polystyrene) class plastics, therefore the processing of these plastics is a problem to be solved.
Due to the product after all consumption of such electric equipment products, HIPS materials are in physical property and ageing properties
Be greatly attenuated so that regenerated polystyrene cannot as virgin resins normal use, shown as when Injection moulded part again
Intensity difference, while it is impossible to meet make large scale electronics again for the heat resistance of material, dimensional stability and creep resistant
The requirement of electric appliance casing.
Therefore, how by obtaining a kind of dimensional stability, heat-resisting and resistance to after waste and old polystyrene plastics regeneration
The HIPS composite of creep properties seems particularly significant.
In view of this, special propose the present invention.
Invention content
One of the objects of the present invention is to provide a kind of recycling sides of waste electric products shell polystyrene plastics
Method can obtain the HIPS composite of high-dimensional stability, heat resistance and creep resistance after this method recycles.
The second object of the present invention is to provide the recycling side of above-mentioned waste electric products shell polystyrene plastics
The poly styrene composite material that method is prepared, the material have outstanding dimensional stability, heat resistance and creep resistance.
The third object of the present invention is to provide the recycling side of above-mentioned waste electric products shell polystyrene plastics
Application of the poly styrene composite material that method is prepared in production electronic product and packaging material.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
In a first aspect, the present invention provides a kind of recoverying and utilizing method of waste electric products shell polystyrene plastics,
Include the following steps：
By mass fraction by 50-70 parts of polystyrene regeneration particle and 2-5 parts of discarded cloth waste, 5-10 parts of activation
Magnesium borate crystal whisker, 10-20 parts of the carbon nanotube of activation, 3-15 parts of acicular wollastonite, 1-2 parts of compatilizer, 1-2 parts of increasing
Through melt blending and cooling granulation after tough dose and 0.5-1 parts of mix lubricant, poly styrene composite material is obtained；
Wherein, polystyrene regeneration particle is that the waste electric products shell polystyrene plastics after being crushed, clean melts
Melt what granulation obtained；Discarded cloth waste is to detach impurity from broken waste electric products shell polystyrene plastics to obtain；
The magnesium borate crystal whisker of activation is prepared by the following method to obtain：
Draw ratio is placed in ultrasonic disperse 3-5min in absolute ethyl alcohol in the magnesium borate crystal whisker of 35-45, obtains dispersion liquid, boron
Content of the sour magnesium whisker in absolute ethyl alcohol is 2-8g/L；Triton X-100 are added into dispersion liquid, Triton X-100 are made
Mass fraction is in the solution of 1-5%, and magnesium borate crystal whisker carries out mixed at high speed 10-20min with solution at 60-70 DEG C, to boric acid
Magnesium whisker carries out the magnesium borate crystal whisker activated after separation is dry；
The carbon nanotube of activation is prepared by the following method to obtain：
Carbon nanotube by draw ratio in 300-800 carries out mixed grinding, the matter of carbon nanotube and modifying agent with modifying agent
Amount is than being 1：(1-5), the carbon nanotube activated；Wherein, modifying agent includes cyclodextrin and ionic liquid, cyclodextrin and ion
The molar ratio of liquid is 2：(0.5-1.5).
Preferably, based on the technical solution of the present invention, polystyrene regeneration particle is prepared by the following method to obtain：
Waste electric products shell polystyrene plastics is recycled, content of beary metal is tested by XRF, to standard compliant useless
It abandons after electronic product casing polystyrene plastics is cleaned, be crushed, cleaned again, wash and dried and carries out melt pelletization, obtain
Polystyrene regenerates particle.
Preferably, based on the technical solution of the present invention, it discards cloth waste and is using preceding progress dusting processing.
Preferably, based on the technical solution of the present invention, the draw ratio of acicular wollastonite be 10-30, grain size 800-
1000 mesh；
Preferably, acicular wollastonite is impregnated using the preceding hydrofluoric acid for being 0.5-2% with mass fraction, soaking time
For 1-3h.
Preferably, based on the technical solution of the present invention, compatilizer include high-density polycthylene grafted maleic anhydride, it is low
Density polyethylene grafted maleic anhydride, linear low density polyethylene grafted maleic anhydride, ethylene propylene copolymer grafted maleic
Acid anhydride, ethylene octene copolymer grafted maleic anhydride or one kind in polypropylene grafted maleic anhydride or at least two combination.
Preferably, based on the technical solution of the present invention, toughener includes that ethylene-hexene co-polymers, Ethylene/Butylene are total
In polymers, ethylene-octene copolymer, ethylene-propylene-octene terpolymer or hydrogenation of ethylene-butadiene-styrene copolymer
One kind or at least two combination.
Preferably, based on the technical solution of the present invention, lubricant include ethylene bis stearic acid amide, erucyl amide,
One kind in zinc stearate or organic silicone oil or at least two combination.
Preferably, based on the technical solution of the present invention, the above method includes the following steps：
(a) mass fraction is pressed by 50-70 parts of polystyrene regeneration particle and 2-5 parts of discarded cloth waste, 10-20 parts of work
The carbon nanotube of change, 3-15 parts of acicular wollastonite, 1-2 parts of compatilizer, 1-2 parts of toughener and 0.5-1 parts of lubrication
Agent mixes, and melt blending is carried out into twin-screw；
(b) magnesium borate crystal whisker of 5-10 parts of activation is mixed with 5-15 parts of binder by mass fraction, into double spiral shells
Bar carries out melt blending together with step (a) component, then squeezes out cooling granulation, obtains poly styrene composite material；
Preferably, twin-screw melt zone temperature is 120-200 DEG C, preferably 120-180 DEG C；Mixing section temperature is 180-220
DEG C, preferably 180-200 DEG C；Metering section temperature is 200-240 DEG C, preferably 200-220 DEG C；Die head temperature is 230-250 DEG C, preferably
230-240℃。
Second aspect, the present invention provides a kind of recycling sides of above-mentioned waste electric products shell polystyrene plastics
The poly styrene composite material that method is prepared.
The third aspect, the present invention provides a kind of recoverying and utilizing method systems of waste electric products shell polystyrene plastics
Application of the standby obtained poly styrene composite material in production electronic product and packaging material.
Compared with the prior art, the present invention has the advantages that：
(1) recoverying and utilizing method of waste electric products shell polystyrene plastics of the present invention by will recycle it is broken,
The polystyrene regeneration particle that electronic product casing waste plastic melt pelletization after removal of impurities obtains is lived with discarded cloth waste, through surface
It is compound to change magnesium borate crystal whisker handle, with draw ratio, carbon nanotube and acicular wollastonite inorganic material, and compounds compatible
New poly styrene composite material is made of melt blending technology for agent, toughener and lubricant, and magnesium borate crystal whisker, carbon are received
The rigidity of mitron and acicular wollastonite inorganic material, dimensional stability and thermal stability and the toughness of high molecular material are mutually tied
It closes, containing elements such as Mg, C, Si in inorganic material, the intensity of material can be promoted.Magnesium borate crystal whisker and carbon nanotube pass through simultaneously
It crosses specific activation method to be handled, the magnesium borate crystal whisker activity after activating by using the method for the present invention is strong, in polyphenyl second
Good dispersion in alkene and strong with the interface binding power of polystyrene, can give full play to the humidification of magnesium borate crystal whisker, carry
The heat resistance of high material.Activating means activated carbon nano-tube by using the present invention not only enables carbon nanotube and polyphenyl
Ethylene has outstanding compatibility and caking property, and carbon nanotube dispersibility is significantly improved, while not destroying carbon nanometer
Pipe conjugated structure will not cause the fracture of carbon nanotube, reduce the draw ratio of carbon nanotube, while wrapped cyclodextrin-ion
The carbon nano tube surface of liquid clathrate clad is adequately protected, and the heat resistance and impact resistance of composite material are improved.It is logical
Cross magnesium borate crystal whisker, the carbon nanotube of activation and the mutual cooperation energy of acicular wollastonite of polystyrene regeneration particle and activation
Enough linear expansion coefficients and shrinking percentage that material is effectively reduced on the basis of other mechanical properties do not decline, it is heat-resisting to improve material
Property, achieve the purpose that dimensionally stable.
(2) verified, by the method for the present invention handle the poly styrene composite material linear expansion coefficient that is prepared and
Shrinking percentage is low, and heat resistance is good, and dimensional stability is high, tensile strength >=50MPa, notch impact strength >=30KJ/m2, linear swollen
Swollen coefficient≤3.0 × 10-5Mm/mm/ DEG C, croop property 0.6-0.8%, dimensional stability is less than 1.3%, is that a kind of high size is steady
Qualitative, high heat-resisting and creep resistant HIPS composite, can be reused for preparing large scale product product.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of recycling profit of waste electric products shell polystyrene plastics is provided
With method, include the following steps：
By mass fraction by 50-70 parts of polystyrene regeneration particle and 2-5 parts of discarded cloth waste, 5-10 parts of activation
Magnesium borate crystal whisker, 10-20 parts of the carbon nanotube of activation, 3-15 parts of acicular wollastonite, 1-2 parts of compatilizer, 1-2 parts of increasing
Through melt blending and cooling granulation after tough dose and 0.5-1 parts of mix lubricant, poly styrene composite material is obtained；Wherein,
Polystyrene regeneration particle is that the waste electric products shell polystyrene plastics melt pelletization after being crushed, clean obtains；
Discarded cloth waste is to detach impurity from broken waste electric products shell polystyrene plastics to obtain；
The magnesium borate crystal whisker of activation is prepared by the following method to obtain：Magnesium borate crystal whisker by draw ratio in 35-45 is placed in
Ultrasonic disperse 3-5min in absolute ethyl alcohol, obtains dispersion liquid, and content of the magnesium borate crystal whisker in absolute ethyl alcohol is 2-8g/L；To point
Triton X-100 are added in dispersion liquid, Triton X-100 mass fractions are made in the solution of 1-5%, magnesium borate crystal whisker and solution
The mixed at high speed 10-20min at 60-70 DEG C, the magnesium borate crystal whisker that magnesium borate crystal whisker activated after separation is dry；
The carbon nanotube of activation is prepared by the following method to obtain：The carbon nanotube in 300-800 and modification by draw ratio
The mass ratio of agent progress mixed grinding, carbon nanotube and modifying agent is 1：(1-5), the carbon nanotube activated；Wherein, modified
Agent includes cyclodextrin and ionic liquid, and the molar ratio of cyclodextrin and ionic liquid is 2：(0.5-1.5).
After the present invention recycles waste polystyrene plastic electronic product casing manufactured polystyrene regeneration particle with it is more
Kind inorganic material is used cooperatively, and a kind of poly styrene composite material of new excellent performance is made using melt blending technology, can
To be reused for making large scale product so that waste plastic is fully recycled.
Raw material includes the polystyrene regeneration particle of 50-70 mass parts and discarded cloth waste, the 5-10 mass parts of 2-5 mass parts
The magnesium borate crystal whisker of activation, the carbon nanotube of activation of 10-20 mass parts, the acicular wollastonite of 3-15 mass parts, 1-2 mass
The compatilizer, the toughener of 1-2 mass parts and the lubricant of 0.5-1 mass parts of part.
Polystyrene regenerates particle
Polystyrene regeneration particle be will be crushed, clean after waste electric products shell polystyrene plastics melt pelletization
It obtains.
Typical polystyrene regeneration particle for example comes from housing of TV set sorting regeneration particle or comes from miscellaneous casing
Regeneration particle after sorting etc..
The polystyrene regeneration typical but non-limiting mass fraction of particle is, for example, 50 parts, 52 parts, 54 parts, 56 parts, 58
Part, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts or 70 parts.
Discarded cloth waste
Discarded cloth waste is to detach impurity from broken waste electric products shell polystyrene plastics to obtain, due to useless
Many impurity, such as metal, cloth waste etc. can be carried in removal process by abandoning plastics, and by screening, detaching after recycling, impurity is picked
It removes, the present invention recycles the discarded cloth waste isolated in removal process directly as raw material.
The discarded typical but non-limiting mass fraction of cloth waste is, for example, 2 parts, 3 parts, 4 parts or 5 parts.
The magnesium borate crystal whisker of activation
Magnesium borate crystal whisker has the advantages that high temperature resistant, good toughness, intensity are high, strong with plastics affinity, advantageous after addition
In the intensity and heat resistance that improve material.
The magnesium borate crystal whisker of the present invention is the magnesium borate crystal whisker after activation, the magnesium borate crystal whisker draw ratio of selection in 35-45,
The source of magnesium borate crystal whisker is not construed as limiting, as long as draw ratio is in 35-45.
Draw ratio is the ratio of length and diameter, and magnesium borate crystal whisker draw ratio is, for example, 35:1、36:1、37:1、38:1、
39:1、40:1、41:1、42:1、43:1、44:1 or 45:1.
There is stronger rigidity, toughness and thermal stability, draw ratio too conference in the magnesium borate crystal whisker of this draw ratio range
Itself and the mixed mobility of resin are influenced, is unfavorable for processing.
The magnesium borate crystal whisker of selection is activated：Ultrasonic disperse 3-5min in absolute ethyl alcohol is first placed it in, such as
3min, 4min or 5min, content of the control magnesium borate crystal whisker in absolute ethyl alcohol are 2-8g/L, for example, 2g/L, 4g/L, 6g/L or
8g/L obtains certain density magnesium borate crystal whisker-absolute ethyl alcohol dispersion liquid, and Triton X-100 are then added into dispersion liquid changes
Property agent, make the mass concentrations of Triton X-100 in ethanol be 1-5%, such as 1%, 2%, 3%, 4% or 5%.Antifungin
Whisker mixed at high speed 10-20min at 60-70 DEG C with the solution after addition modifier, then detaches magnesium borate crystal whisker
It is dry, the magnesium borate crystal whisker activated.
Magnesium borate crystal whisker can be carried out with the solution mixed at high speed after addition modifier in high-speed mixer, mixing rate
Up to 1000r/min or more.Mixing temperature is, for example, 60 DEG C, 65 DEG C or 70 DEG C, incorporation time be, for example, 10min, 15min or
20min。
Triton X-100 are a kind of nonionic surfactants, have phenyl ring and Long carbon chain in structure, through Triton X-
The modified magnesium borate crystal whisker surface neutral in 100 surfaces, and the dispersibility between magnesium borate crystal whisker can be increased, so that whisker is existed
It is spaced from each other and is uniformly distributed in matrix, while there are phenyl ring in modified whisker surface texture, can enhance itself and polyphenyl
The active force of ethylene makes it fully be infiltrated by polystyrene.
Magnesium borate crystal whisker activity after being activated by using the method for the present invention is strong, good dispersion in polystyrene and with
The interface binding power of polystyrene is strong, can give full play to the humidification of magnesium borate crystal whisker, improves the heat resistance of material.
The typical but non-limiting mass fraction of magnesium borate crystal whisker of activation is, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10
Part.
The carbon nanotube of activation
The carbon nanotube of the present invention is the carbon nanotube after activation, and the carbon nanotube draw ratio of selection is in 300-800, to carbon
The source of nanotube is not construed as limiting, as long as draw ratio is in 300-800, for example, 300:1、350:1、400:1、450:1、
500:1、550:1、600:1、650:1、700:1、750:1 or 800:1.
Good in the carbon nanotube performance of this draw ratio range, draw ratio is easy greatly very much winding, is unfavorable for post-production.
Carbon nanotube has very high draw ratio, certain rigid and good dimensional stability, and light-weight, but due to
There are stronger Van der Waals force and specific surface energy are big between carbon nanotube, dispersibility and poor with the compatibility of matrix,
It tends to reunite or wind, its effect cannot be given full play to, it is therefore desirable to activate to it.
The present invention is to carry out mixed grinding using modifying agent and its to the activation method of carbon nanotube, and modifying agent includes ring paste
The molar ratio of essence and ionic liquid, cyclodextrin and ionic liquid is 2：(0.5-1.5), such as 2：0.5、2：1 or 2：1.5, carbon is received
The mass ratio of mitron and modifying agent is 1：(1-5), such as 1：1、1：2、1：3、1：4 or 1：5.
Typical but non-limiting cyclodextrin is, for example, beta-cyclodextrin, and typical but non-limiting ionic liquid is, for example, miaow
Azole, piperidines, pyroles, quaternary amines or amides ionic liquid etc..
Preferably, ionic liquid includes 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-four
Borofluoride, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazoles-hexafluorophosphate,
1- propyl -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1-
Methylimidazole-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- methylimidazoles-bis trifluoromethyl
Sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl -1- methylpyrrolidin- double three
Methyl fluoride sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis- three
One kind or at least two in methyl fluoride sulfimide salt or N- methyl butyls piperidines-bis trifluoromethyl sulfimide salt.
Modified carbon nanotubes are coated by cyclodextrin and ionic liquid, and cyclodextrin has hydrophobic cavity, can include ion
Liquid forms cyclodextrin-ionic liquid inclusion compound, due to ionic liquid band like charges itself, the carbon nanotube table after cladding
Face band like charges, improve carbon nanotube dispersibility in polystyrene, at the same the clathration of cyclodextrin can protect from
Sub- liquid, prevent in process surface coating layer fall off, cyclodextrin-ionic liquid inclusion compound clad of formation is in gel
Shape, caking property are good.
Activating means step by using the present invention is few, efficient, and carbon nanotube and polystyrene is not only enable to have
There are outstanding compatibility and binder, and carbon nanotube dispersibility is significantly improved, while destroying carbon nanometer tube is not conjugated
Structure will not cause the fracture of carbon nanotube, reduce the draw ratio of carbon nanotube, while wrapped cyclodextrin-ionic liquid packet
The carbon nano tube surface for closing object clad is adequately protected, and the heat resistance and impact resistance of composite material are improved.
The typical but non-limiting mass fraction of carbon nanotube of activation is, for example, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts
Or 20 parts.
Acicular wollastonite
Acicular wollastonite finger-type shape is in acicular wollastonite, has high length-diameter ratio, and the shock resistance for being conducive to improve material is strong
Degree, enhancing mobility and reinforcement material stiffness and strength and structural stability.
The typical but non-limiting mass parts of acicular wollastonite are, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10
Part, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts.
Compatilizer
Compatilizer refers to be promoted the substance of compatibility between polystyrene and inorganic material.
Typical but non-limiting compatilizer is, for example, high-density polycthylene grafted maleic anhydride, grafted low density polyethylene
Maleic anhydride, linear low density polyethylene grafted maleic anhydride, ethylene propylene copolymer grafted maleic anhydride, ethylene octene copolymerization
Object grafted maleic anhydride or polypropylene grafted maleic anhydride etc..
The typical but non-limiting mass fraction of compatilizer is, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts.
Compatibility between polystyrene and above-mentioned inorganic material can be promoted by preferably selecting maleic anhydride graft compatilizer.
Toughener
Typical but non-limiting toughener is, for example, ethylene-hexene co-polymers, ethylene-butene copolymer, ethylene-octene
Copolymer, ethylene-propylene-octene terpolymer or hydrogenation of ethylene-butadiene-styrene copolymer etc..
The typical but non-limiting mass fraction of toughener is, for example, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts.
By adding toughener, toughness of material can be promoted, alleviates polystyrene and regenerates what particle aging rear toughness declined
Defect.
Lubricant
Typical but non-limiting lubricant is, for example, ethylene bis stearic acid amide, erucyl amide, zinc stearate or organic
Silicone oil etc..
The typical but non-limiting mass fraction of lubricant is, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1
Part.
The lubricity of material in process can be promoted by adding lubricant.
The recoverying and utilizing method of waste electric products shell polystyrene plastics of the present invention passes through broken, the removal of impurities that will recycle
Polystyrene that electronic product casing waste plastic melt pelletization afterwards obtains regeneration particle with discarded cloth waste, through surface active at
Reason, magnesium borate crystal whisker with draw ratio, carbon nanotube and acicular wollastonite inorganic material it is compound, and compound compatilizer,
New poly styrene composite material is made of melt blending technology for toughener and lubricant, by magnesium borate crystal whisker, carbon nanotube
And rigidity, dimensional stability and the thermal stability of acicular wollastonite inorganic material are combined with the toughness of high molecular material, nothing
Containing elements such as Mg, C, Si in machine material, the intensity of material can be promoted.Magnesium borate crystal whisker and carbon nanotube are passed through specific simultaneously
Activation method handled, the effect of magnesium borate crystal whisker and carbon nanotube in the material can be given full play to after processing, is passed through
Polystyrene regenerates the phase of particle and discarded cloth waste, the magnesium borate crystal whisker of activation, the carbon nanotube of activation and acicular wollastonite
Mutually cooperation can effectively reduce linear expansion coefficient and the contraction of material on the basis of not changing other mechanical properties and not declining
Rate improves material thermal resistance, achievees the purpose that dimensionally stable.It is verified, handle the polyphenyl being prepared by the method for the present invention
The linear coefficient of expansion of ethylene composite material and shrinking percentage are low, and heat resistance is good, and dimensional stability is high, is a kind of high dimensionally stable
Property, high heat-resisting and creep resistant HIPS composite, can be reused for preparing large scale product product.
It should be noted that polystyrene of the present invention regeneration particle, discarded cloth waste, activation magnesium borate crystal whisker, activate
Proportionate relationship between carbon nanotube, acicular wollastonite, compatilizer, toughener and lubricant is not arbitrary, but is passed through
Determination is explored repeatedly, and the ratio between each component has a major impact material property.If for example, activation magnesium borate crystal whisker,
Carbon nanotube, the acicular wollastonite dosage of activation are unreasonable, will cause the dimensional stability of material that preferable level is not achieved.
In a preferred embodiment, polystyrene regeneration particle is prepared by the following method to obtain：
Waste electric products shell polystyrene plastics is recycled, content of beary metal is tested by XRF, to standard compliant useless
It abandons after electronic product casing polystyrene plastics is cleaned, be crushed, cleaned again, wash and dried and carries out melt pelletization, obtain
Polystyrene regenerates particle.
XRF tests refer to X-ray fluorescence spectra analysis (X Ray Fluorescence), and the weight of plastic shell is measured with it
Tenor is directly reported if the noxious materials such as heavy metal are more than relevant national standard (such as GB/T 30102-2013)
It is useless, it is no longer accordingly recycled, is transferred to other approach and carries out respective handling (such as burning disposal), only standard compliant material
Material just carries out recycling.
By being cleaned, be crushed to the waste electric products shell polystyrene plastics after recycling, cleaned again, washed and
The processing such as dry, so as to get the good polystyrene of performance regenerate particle.
In a preferred embodiment, it discards cloth waste and is using preceding progress dusting processing.
In order to facilitate granulation, discarded cloth waste is subjected to dusting processing, dusting processing refers to crushing discarded cloth waste, is obtained
To powder.
Cloth waste is discarded by the way that powdery is added, so that cloth waste is fully utilized, further functions as filling effect.
In a preferred embodiment, the draw ratio of acicular wollastonite is 10-30, grain size is 800-1000 mesh.
The draw ratio of acicular wollastonite is, for example, 10:1、12:1、14:1、16:1、18:1、20:1、22:1、24:1、26:1、
28:1 or 30:1.
The grain size of acicular wollastonite is, for example, 800 mesh, 900 mesh or 1000 mesh.
By selecting the acicular wollastonite of certain draw ratio and grain size that can preferably play the shock resistance of acicular wollastonite
Strength character.
In a preferred embodiment, acicular wollastonite is using the preceding hydrofluoric acid for being 0.5-2% with mass fraction
It is impregnated, soaking time 1-3h.
Hydrofluoric acid mass fraction is, for example, 0.5%, 1%, 1.5% or 2%；Soaking time is, for example, 1h, 2h or 3h.
It can make acicular wollastonite surface that micropore be presented by hydrofluoric acid dips, improve its effect with polystyrene, and
And the F ion on surface can be such that acicular wollastonite more disperses, to improve the effect of acicular wollastonite in polystyrene, into
One step promotes material property.
In a preferred embodiment, the recoverying and utilizing method of waste electric products shell polystyrene plastics includes
Following steps：
(a) mass fraction is pressed by 50-70 parts of polystyrene regeneration particle and 2-5 parts of discarded cloth waste, 10-20 parts of work
The carbon nanotube of change, 3-15 parts of acicular wollastonite, 1-2 parts of compatilizer, 1-2 parts of toughener and 0.5-1 parts of lubrication
Agent mixes, and melt blending is carried out into twin-screw；
(b) magnesium borate crystal whisker of 5-10 parts of activation is mixed with 5-15 parts of binder by mass fraction, into double spiral shells
Bar carries out melt blending together with step (a) component, then squeezes out cooling granulation, obtains poly styrene composite material；
Typical but non-limiting binder is, for example, polyvinyl alcohol, polyvinyl butyral or acrylic resin etc..
Since magnesium borate crystal whisker apparent density is light, it is also easy to produce that " bridge formation ", mobility is bad and drops with screw rod propelling method feeding
Low addition effect influences addition and dispersing uniformity of the whisker in macromolecule, therefore, first uses binder and magnesium borate crystal whisker
It is mixed, then keeps the dispersion of whisker adition process more uniform with other components mixing granulation again, promote material after processing
Performance.
Preferably, twin-screw melt zone temperature is 120-200 DEG C, preferably 120-180 DEG C；Mixing section temperature is 180-220
DEG C, preferably 180-200 DEG C；Metering section temperature is 200-240 DEG C, preferably 200-220 DEG C；Die head temperature is 230-250 DEG C, preferably
230-240℃。
Twin-screw melt zone temperature is, for example, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C or 200 DEG C；Mixing section temperature is, for example,
180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C or 220 DEG C；Metering section temperature is, for example, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C or 240
℃；Die head temperature is, for example, 230 DEG C, 240 DEG C or 250 DEG C.
By controlling twin-screw melting extrusion stage each temperature, compound of the good polystyrene of formability can be obtained
Grain.
According to the second aspect of the invention, a kind of returning for above-mentioned waste electric products shell polystyrene plastics is provided
Receive the poly styrene composite material being prepared using method.
Handling the poly styrene composite material that is prepared by the method for the present invention has outstanding dimensional stability, heat-resisting
Property and creep resistance, linear expansion coefficient and shrinking percentage it is low, heat resistance is good, and dimensional stability is high, tensile strength of material >=
50MPa, notch impact strength >=30KJ/m2, linear expansion coefficient≤3.0 × 10-5DEG C, croop property 0.6-0.8%, size is steady
It is qualitative to be less than 1.3.
According to the third aspect of the present invention, a kind of returning for above-mentioned waste electric products shell polystyrene plastics is provided
Receive application of the poly styrene composite material being prepared using method in production electronic product and packaging material.
Typical but non-limiting electronic product is, for example, television set, printer, sound equipment electric appliance or computer.
Due to obtained HIPS composite be it is a kind of there is high-dimensional stability, high heat-resisting and creep resistant material,
It can be reused for preparing large scale product product, have a extensive future.
In order to further appreciate that the present invention, the method for the present invention and effect are done further in detail with reference to specific embodiment
Explanation.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or
Production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
The raw material information that embodiment is related to is as follows：
Polystyrene regenerates particle：Come from housing of TV set polystyrene plastics sorting regeneration particle；
Discarded cloth waste crushed material：Come from recycling housing of TV set polystyrene plastics therefrom detach impurity obtain it is discarded broken
What cloth obtained after crushing；
Magnesium borate crystal whisker：Draw ratio 35-45；
Carbon nanotube：Draw ratio 300-800；
Acicular wollastonite：Draw ratio is 10-30, grain size 800-1000 mesh.
Embodiment 1
A kind of recoverying and utilizing method of waste electric products shell polystyrene plastics, includes the following steps：
(a) magnesium borate crystal whisker of activation is prepared：Magnesium borate crystal whisker is placed in ultrasonic disperse 3min in absolute ethyl alcohol, is divided
Dispersion liquid, content of the magnesium borate crystal whisker in absolute ethyl alcohol are 8g/L；Triton X-100 are added into dispersion liquid, Triton is made
Solution of the X-100 mass fractions 1%, magnesium borate crystal whisker and solution mixed at high speed 20min at 60 DEG C, to magnesium borate crystal whisker into
The magnesium borate crystal whisker activated after row separation is dry；
(b) carbon nanotube of activation is prepared：Carbon nanotube and modifying agent are subjected to mixed grinding, carbon nanotube and modifying agent
Mass ratio be 1：1, the carbon nanotube activated；Wherein, modifying agent includes cyclodextrin and 1- ethyl-3-methylimidazoles-six
The molar ratio of fluorophosphate, cyclodextrin and 1- ethyl-3-methylimidazoles-hexafluorophosphate is 2：1；
(c) acicular wollastonite of activation is prepared：Acicular wollastonite is soaked in the hydrofluoric acid that mass fraction is 0.5%
Bubble, soaking time 3h, the acicular wollastonite activated；
(d) poly styrene composite material is prepared：50 parts of polystyrene regeneration particle is discarded with 5 parts by mass fraction
Cloth waste crushed material, the carbon nanotube of 10 parts of activation, the acicular wollastonite of 15 parts of activation, 1 part of ethylene propylene copolymer connect
Branch maleic anhydride, 2 parts of ethylene-hexene co-polymers and the mixing of 0.5 part of ethylene bis stearic acid amide, carry out into twin-screw
Melt blending；By mass fraction by the magnesium borate crystal whisker of 10 parts of activation and 5 parts of polyvinyl alcohol, into twin-screw with
Upper component carries out melt blending together, then squeezes out cooling granulation, obtains poly styrene composite material；Wherein, twin-screw melts
Duan Wendu is 120 DEG C；Mixing section temperature is 180 DEG C；Metering section temperature is 200 DEG C；Die head temperature is 230 DEG C.
Embodiment 2
A kind of recoverying and utilizing method of waste electric products shell polystyrene plastics, includes the following steps：
(a) magnesium borate crystal whisker of activation is prepared：Magnesium borate crystal whisker is placed in ultrasonic disperse 5min in absolute ethyl alcohol, is divided
Dispersion liquid, content of the magnesium borate crystal whisker in absolute ethyl alcohol are 2g/L；Triton X-100 are added into dispersion liquid, Triton is made
Solution of the X-100 mass fractions 5%, magnesium borate crystal whisker and solution mixed at high speed 10min at 70 DEG C, to magnesium borate crystal whisker into
The magnesium borate crystal whisker activated after row separation is dry；
(b) carbon nanotube of activation is prepared：Carbon nanotube and modifying agent are subjected to mixed grinding, carbon nanotube and modifying agent
Mass ratio be 1：5, the carbon nanotube activated；Wherein, modifying agent includes cyclodextrin and 1- ethyl-3-methylimidazoles-four
The molar ratio of borofluoride, cyclodextrin and 1- ethyl-3-methylimidazoles-tetrafluoroborate is 2：0.5；
(c) acicular wollastonite of activation is prepared：Acicular wollastonite is soaked in the hydrofluoric acid that mass fraction is 1%
Bubble, soaking time 2h, the acicular wollastonite activated；
(d) poly styrene composite material is prepared：70 parts of polystyrene regeneration particle is discarded with 2 parts by mass fraction
Cloth waste crushed material, the carbon nanotube of 20 parts of activation, the acicular wollastonite of 3 parts of activation, the grafting of 2 parts of ethylene octene copolymer
Maleic anhydride, 1 part of ethylene-butene copolymer and the mixing of 1 part of zinc stearate, melt blending is carried out into twin-screw；It presses
Mass fraction is by the magnesium borate crystal whisker of 5 parts of activation and 15 parts of polyvinyl alcohol, into twin-screw together with the above component
Melt blending is carried out, cooling granulation is then squeezed out, obtains poly styrene composite material；Wherein, twin-screw melt zone temperature is 200
℃；Mixing section temperature is 220 DEG C；Metering section temperature is 240 DEG C；Die head temperature is 250 DEG C.
Embodiment 3
A kind of recoverying and utilizing method of waste electric products shell polystyrene plastics, includes the following steps：
(a) magnesium borate crystal whisker of activation is prepared：Magnesium borate crystal whisker is placed in ultrasonic disperse 4min in absolute ethyl alcohol, is divided
Dispersion liquid, content of the magnesium borate crystal whisker in absolute ethyl alcohol are 5g/L；Triton X-100 are added into dispersion liquid, Triton is made
Solution of the X-100 mass fractions 3%, magnesium borate crystal whisker and solution mixed at high speed 15min at 65 DEG C, to magnesium borate crystal whisker into
The magnesium borate crystal whisker activated after row separation is dry；
(b) carbon nanotube of activation is prepared：Carbon nanotube and modifying agent are subjected to mixed grinding, carbon nanotube and modifying agent
Mass ratio be 1：3, the carbon nanotube activated；Wherein, modifying agent includes that cyclodextrin and 1- ethyl-3-methylimidazoles-are bis-
The molar ratio of trifluoromethanesulp-onyl -onyl imide salt, cyclodextrin and 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt is 2：
1.5；
(c) acicular wollastonite of activation is prepared：Acicular wollastonite is soaked in the hydrofluoric acid that mass fraction is 2%
Bubble, soaking time 1h, the acicular wollastonite activated；
(d) poly styrene composite material is prepared：60 parts of polystyrene regeneration particle is discarded with 4 parts by mass fraction
Cloth waste crushed material, the carbon nanotube of 15 parts of activation, the acicular wollastonite of 9 parts of activation, 1.5 parts of polypropylene grafted maleic acid
Acid anhydride, 1.5 parts of ethylene-octene copolymer and the mixing of 0.8 part of organic silicone oil, melt blending is carried out into twin-screw；By matter
Number is measured by the magnesium borate crystal whisker of 8 parts of activation and 8 parts of polyvinyl alcohol, is carried out together with the above component into twin-screw
Then melt blending squeezes out cooling granulation, obtain poly styrene composite material；Wherein, twin-screw melt zone temperature is 180 DEG C；
Mixing section temperature is 200 DEG C；Metering section temperature is 220 DEG C；Die head temperature is 240 DEG C.
Embodiment 4
The present embodiment and embodiment 1 difference lies in, acicular wollastonite without activation, that is, is free of step (c) using preceding,
Step (d) directly uses acicular wollastonite, remaining is the same as embodiment 1.
Embodiment 5
The present embodiment and embodiment 1 do not mixed with binder difference lies in the magnesium borate crystal whisker of, step (d) activation after again
Charging, but enter twin-screw together with other components, it specifically includes：
50 parts of polystyrene is regenerated into particle and 5 parts of discarded cloth waste crushed material, 10 parts of activation by mass fraction
Magnesium borate crystal whisker, the carbon nanotube of 10 parts of activation, the acicular wollastonite of 15 parts of activation, 1 part of ethylene propylene copolymer connect
Branch maleic anhydride, 2 parts of ethylene-hexene co-polymers and the mixing of 0.5 part of ethylene bis stearic acid amide, carry out into twin-screw
Then melt blending squeezes out cooling granulation, obtain poly styrene composite material, remaining is the same as embodiment 1.
Embodiment 6
Difference lies in step (d) twin-screw extrusion condition is different with embodiment 1 for the present embodiment：Melt zone temperature is 100
℃；Mixing section temperature is 150 DEG C；Metering section temperature is 180 DEG C；Die head temperature is 280 DEG C, remaining is the same as embodiment 1.
Comparative example 1
Difference lies in be free of step (a), the antifungin without activation is brilliant in step (d) to this comparative example with embodiment 1
Must, remaining is the same as embodiment 1.
Comparative example 2
This comparative example and embodiment 1 difference lies in, be free of step (b), the carbon nanotube without activation in step (d),
Remaining is the same as embodiment 1.
Comparative example 3
Difference lies in be free of step (c), the needle-shaped silicon ash of activation be free of in step (d) this comparative example with embodiment 1
Stone, remaining is the same as embodiment 1.
Comparative example 4
A kind of recoverying and utilizing method of waste electric products shell polystyrene plastics, includes the following steps：
Prepare poly styrene composite material：It is by mass fraction that 50 parts of polystyrene regeneration particle and 5 parts discard is broken
Cloth crushed material, 10 parts of nano-calcium carbonate, 15 parts of wollastonite, 1 part of ethylene propylene copolymer grafted maleic anhydride, 2 parts
Ethylene-hexene co-polymers and the mixing of 0.5 part of ethylene bis stearic acid amide, melt blending is carried out into twin-screw；By quality
Number together with the above component melt altogether by 10 parts of calcium sulfate crystal whiskers and 5 parts of polyvinyl alcohol, into twin-screw
It is mixed, cooling granulation is then squeezed out, poly styrene composite material is obtained；Wherein, twin-screw melt zone temperature is 120 DEG C；Mixing section
Temperature is 180 DEG C；Metering section temperature is 200 DEG C；Die head temperature is 230 DEG C.
Comparative example 5
The present embodiment and embodiment 1 difference lies in, magnesium borate crystal whisker without activation, that is, is free of step (a) using preceding,
Step (d) directly uses magnesium borate crystal whisker, remaining is the same as embodiment 1.
Comparative example 6
Difference lies in carbon nanotube without activation, that is, is free of step (b), step to the present embodiment using preceding with embodiment 1
Suddenly (d) directly uses carbon nanotube, remaining is the same as embodiment 1.
Comparative example 7
Difference lies in step (a) is different to the activation method of magnesium borate crystal whisker, specific to wrap with embodiment 1 for the present embodiment
It includes：Magnesium borate crystal whisker is placed in ultrasonic disperse 3min in absolute ethyl alcohol, obtains dispersion liquid, magnesium borate crystal whisker is in absolute ethyl alcohol
Content is 8g/L；Silane resin acceptor kh-550 is added into dispersion liquid, silane resin acceptor kh-550 mass fraction is made 1%
Solution, magnesium borate crystal whisker and solution mixed at high speed 20min at 60 DEG C to magnesium borate crystal whisker activated after separation is dry
Magnesium borate crystal whisker, remaining is the same as embodiment 1.
Comparative example 8
Difference lies in step (b) is different to the activation method of carbon nanotube, specifically includes with embodiment 1 for the present embodiment：
By carbon nanotube and silane resin acceptor kh-550 progress mixed grinding, the mass ratio of carbon nanotube and silane resin acceptor kh-550 is
1：1, the carbon nanotube activated, remaining is the same as embodiment 1.
Comparative example 9
Difference lies in step (b) is different to the activation method of carbon nanotube, specifically includes with embodiment 1 for the present embodiment：
Carbon nanotube and 1- ethyl-3-methylimidazoles-hexafluorophosphate are subjected to mixed grinding, carbon nanotube and 1- ethyl -3- methyl
The mass ratio of imidazoles-hexafluorophosphate is 1：1, the carbon nanotube activated, remaining is the same as embodiment 1.
Comparative example 10
Difference lies in step (c) is different to the activation method of acicular wollastonite, specific to wrap with embodiment 1 for the present embodiment
It includes：Acicular wollastonite is impregnated in the hydrochloric acid that mass fraction is 0.5%, soaking time 3h, what is activated is needle-shaped
Wollastonite, remaining is the same as embodiment 1.
Comparative example 11
Difference lies in the magnesium borate crystal whisker for the use of draw ratio being 20, remaining is the same as embodiment 1 with embodiment 1 for the present embodiment.
Comparative example 12
Difference lies in the magnesium borate crystal whisker for the use of draw ratio being 50, remaining is the same as embodiment 1 with embodiment 1 for the present embodiment.
Comparative example 13
Difference lies in the carbon nanotube for the use of draw ratio being 200, remaining is the same as embodiment 1 with embodiment 1 for the present embodiment.
Comparative example 14
Difference lies in the carbon nanotube for the use of draw ratio being 1000, remaining is the same as embodiment 1 with embodiment 1 for the present embodiment.
Comparative example 15
The present embodiment and embodiment 1 difference lies in, the acicular wollastonite that using draw ratio be 5, grain size is 600 mesh,
Remaining same embodiment 1.
Test example
The obtained poly styrene composite material of embodiment 1-6 and comparative example 1-15 is tested for the property, test method
It is as follows：
Tensile strength：ISO 527/2；
Izod notched impact strength：ISO 180；
Linear expansion coefficient：ISO 11359；
Dimensional stability：(or hanging) is kept flat after graticule distance as defined in first marking detected sample on surface examining
In measuring tank；After time as defined in being stored in set point of temperature, it is cooled to room temperature in case, detects graticule distance immediately.Then plastics try
The graticule size changing rate of sample is：S1=(L1-L0)/L0S in × 100% formula1Sample change rate, %；L0Initial (the examination of sample graticule
Before testing) long, mm；L1Long, mm after the experiment of sample graticule；
Croop property：Using Hakke rheometers using croop property when 120 DEG C of test material of Inertia Based on Torsion Pendulum Method progress, 2min.
Test result is shown in Table 1.
Table 1
Table 1 the result shows that, poly styrene composite material that the present invention obtains rigidity and toughness are preferable, linear expansion coefficient
Low with shrinking percentage, heat resistance is good, and dimensional stability is high, tensile strength >=50MPa, notch impact strength >=30KJ/m2, linearly
The coefficient of expansion≤3.0 × 10-5DEG C, croop property 0.6-0.8%, dimensional stability is less than 1.3%.
Comparative example 1 compared with Example 1, be free of magnesium borate crystal whisker, comparative example 2 compared with Example 1, not carbon containing nanometer
Pipe, comparative example 3 compared with Example 1, are free of acicular wollastonite, tensile strength, linear expansion coefficient and the ruler of obtained material
Very little performance for stability decreases, it can be seen that, by the way that magnesium borate crystal whisker, carbon nanotube and acicular wollastonite and polyphenyl is added
The mutual cooperation of ethylene can promote the intensity, dimensional stability and thermal stability of material.
The inorganic material that comparative example 4 uses for nano-calcium carbonate, wollastonite and calcium sulfate crystal whiskers, the tensile strength of material,
It is good that linear expansion coefficient and dimensional stability are obviously not so good as effect of the present invention, it can be seen that the present invention is not only by being added boric acid
Magnesium whisker, carbon nanotube and acicular wollastonite inorganic material, and by being activated to inorganic material, can significantly improve
Material stiffness.
Compared with Example 1, magnesium borate crystal whisker is not activated for comparative example 5, comparative example 6 compared with Example 1, carbon nanotube
Not activated, tensile strength, linear expansion coefficient and the dimensional stability of material can not obtain preferable level.
Comparative example 7 compared with Example 1, using silane coupling agent activates magnesium borate crystal whisker, comparative example 8 and implementation
Example 1 is compared, and activation method is different from the present invention, and is activated to carbon nanotube using silane coupling agent, and comparative example 9 individually uses
Ionic liquid carries out cladding activation, and tensile strength, linear expansion coefficient and the dimensional stability of material are declined, this be by
In the activator and activation method difference of use, causes activation effect bad, seriously affect magnesium borate crystal whisker and carbon nanotube exists
Effect in polystyrene.Comparative example 10 uses salt acid soak to acicular wollastonite, and the effect for obtaining material is also not so good as embodiment
1, it can be seen that by using specific activation method, obtain preferable activation effect, can give full play to magnesium borate crystal whisker,
The effect of carbon nanotube and acicular wollastonite inorganic material in polystyrene.
The magnesium borate crystal whisker draw ratio that comparative example 11-12 is used not within the scope of the present invention, the carbon that comparative example 13-14 is used
Nanotube draw ratio not within the scope of the present invention, the acicular wollastonite draw ratio that comparative example 15 uses not within the scope of the present invention,
Material property cannot obtain desirable level, it can be seen that, using each component and polystyrene within the scope of draw ratio of the present invention
Cooperation, could obtain better effect.
Further analysis, compared with Example 4, using the acicular wollastonite after activation, material property is more preferable for embodiment 1,
Magnesium borate crystal whisker is first mixed with unclassified stores with binder mixed feeding again when embodiment 5 is processed, and acquisition material property is more preferable, this
It is to be mixed together the easy addition for influencing whisker in macromolecule since magnesium borate crystal whisker density is lighter with unclassified stores and divide
Uniformity is dissipated, therefore effect of the whisker in macromolecule can be promoted using this kind of feeding manner.The twin-screw that embodiment 6 uses squeezes
Go out temperature in the preferred range, processing obtains that material processing forming is more preferable, and performance is more excellent.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of recoverying and utilizing method of waste electric products shell polystyrene plastics, which is characterized in that include the following steps：
50-70 parts of polystyrene is regenerated into particle and 2-5 parts of discarded cloth waste, the boric acid of 5-10 parts of activation by mass fraction
Magnesium whisker, 10-20 parts of the carbon nanotube of activation, 3-15 parts of acicular wollastonite, 1-2 parts of compatilizer, 1-2 parts of toughener
And poly styrene composite material is obtained through melt blending and cooling granulation after 0.5-1 parts of mix lubricant；
Wherein, polystyrene regeneration particle is that the waste electric products shell polystyrene plastics melting after being crushed, clean is made
What grain obtained；Discarded cloth waste is to detach impurity from broken waste electric products shell polystyrene plastics to obtain；
The magnesium borate crystal whisker of activation is prepared by the following method to obtain：
Draw ratio is placed in ultrasonic disperse 3-5min in absolute ethyl alcohol in the magnesium borate crystal whisker of 35-45, obtains dispersion liquid, antifungin
Content of the whisker in absolute ethyl alcohol is 2-8g/L；Triton X-100 are added into dispersion liquid, Triton X-100 mass is made
Score is in the solution of 1-5%, magnesium borate crystal whisker and solution mixed at high speed 10-20min at 60-70 DEG C, to magnesium borate crystal whisker into
The magnesium borate crystal whisker activated after row separation is dry；
The carbon nanotube of activation is prepared by the following method to obtain：
Carbon nanotube by draw ratio in 300-800 carries out mixed grinding, the mass ratio of carbon nanotube and modifying agent with modifying agent
It is 1：(1-5), the carbon nanotube activated；Wherein, modifying agent includes cyclodextrin and ionic liquid, cyclodextrin and ionic liquid
Molar ratio be 2：(0.5-1.5).
2. the recoverying and utilizing method of waste electric products shell polystyrene plastics according to claim 1, feature exist
In polystyrene regeneration particle is prepared by the following method to obtain：
Waste electric products shell polystyrene plastics is recycled, content of beary metal is tested by XRF, to standard compliant discarded electricity
Sub- product casing polystyrene plastics carries out melt pelletization after being cleaned, be crushed, cleaned again, wash and being dried, and obtains polyphenyl
Ethylene regenerates particle.
3. the recoverying and utilizing method of waste electric products shell polystyrene plastics according to claim 1, feature exist
In discarded cloth waste is using preceding progress dusting processing.
4. the recoverying and utilizing method of waste electric products shell polystyrene plastics according to claim 1, feature exist
In the draw ratio of acicular wollastonite is 10-30, grain size is 800-1000 mesh；
Preferably, acicular wollastonite is impregnated using the preceding hydrofluoric acid for being 0.5-2% with mass fraction, soaking time 1-
3h。
5. according to the recoverying and utilizing method of claim 1-4 any one of them waste electric products shell polystyrene plastics,
It is characterized in that, compatilizer include high-density polycthylene grafted maleic anhydride, it is grafted low density polyethylene maleic anhydride, linear low
Density polyethylene grafted maleic anhydride, ethylene propylene copolymer grafted maleic anhydride, ethylene octene copolymer grafted maleic anhydride
One kind in polypropylene grafted maleic anhydride or at least two combination.
6. according to the recoverying and utilizing method of claim 1-4 any one of them waste electric products shell polystyrene plastics,
It is characterized in that, toughener includes ethylene-hexene co-polymers, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-the third
Alkene-octene terpolymer or one kind in hydrogenation of ethylene-butadiene-styrene copolymer or at least two combination.
7. according to the recoverying and utilizing method of claim 1-4 any one of them waste electric products shell polystyrene plastics,
It is characterized in that, lubricant includes one kind in ethylene bis stearic acid amide, erucyl amide, zinc stearate or organic silicone oil or extremely
Few two kinds of combination.
8. according to the recoverying and utilizing method of claim 1-4 any one of them waste electric products shell polystyrene plastics,
It is characterized by comprising the following steps：
(a) it presses mass fraction and 50-70 part of polystyrene is regenerated into particle and 2-5 parts of discarded cloth waste, 10-20 parts of activation
Carbon nanotube, 3-15 parts of acicular wollastonite, 1-2 parts of compatilizer, 1-2 parts of toughener and 0.5-1 parts of lubricant is mixed
It closes, melt blending is carried out into twin-screw；
(b) magnesium borate crystal whisker of 5-10 parts of activation is mixed with 5-15 parts of binder by mass fraction, into twin-screw with
Step (a) component carries out melt blending together, then squeezes out cooling granulation, obtains poly styrene composite material；
Preferably, twin-screw melt zone temperature is 120-200 DEG C, preferably 120-180 DEG C；Mixing section temperature is 180-220 DEG C, excellent
Select 180-200 DEG C；Metering section temperature is 200-240 DEG C, preferably 200-220 DEG C；Die head temperature is 230-250 DEG C, preferably 230-
240℃。
9. using the recoverying and utilizing method system of claim 1-8 any one of them waste electric products shell polystyrene plastics
Standby obtained poly styrene composite material.
10. using the recoverying and utilizing method of claim 1-8 any one of them waste electric products shell polystyrene plastics
Application of the poly styrene composite material being prepared in production electronic product and packaging material.
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| CN115386176A (en) * | 2022-10-27 | 2022-11-25 | 汕头市华麟塑化有限公司 | Preparation method of high impact-resistant creep-resistant polystyrene |
| US11807746B2 (en) | 2021-08-05 | 2023-11-07 | Industrial Technology Research Institute | Impact-resistant polystyrene resin |
| WO2023218220A1 (en) * | 2022-05-10 | 2023-11-16 | Azuola Andrei Gaggion | High temperature repolymerization recycling and plastics |
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