CN107057141B - A kind of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing butadiene-styrene rubber and preparation method thereof - Google Patents
A kind of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing butadiene-styrene rubber and preparation method thereof Download PDFInfo
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- CN107057141B CN107057141B CN201710304085.6A CN201710304085A CN107057141B CN 107057141 B CN107057141 B CN 107057141B CN 201710304085 A CN201710304085 A CN 201710304085A CN 107057141 B CN107057141 B CN 107057141B
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The present invention provides a kind of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing styrene-butadiene rubber, and provides the preparation method of above-mentioned material.Refinement and surface acid activation process are carried out to discarded printed circuit boards non-metal powder first, and in surface grafting polystyrene, discarded printed circuit boards non-metal powder grafted polystyrene hybrid particle is made；After rubber compound is made in proportion in discarded printed circuit boards non-metal powder grafted polystyrene hybrid particle, butadiene-styrene rubber and auxiliary agent, butadiene-styrene rubber product is made in final vulcanization.The present invention is using discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle as filler filled styrene butadiene rubber, not only reduce the agglomeration of discarded printed circuit boards non-metal powder, and the two compatibility is effectively promoted, to improve the mechanical strength of butadiene-styrene rubber；The production cost of product is reduced, there is certain economic value；Waste circuit board non-metal powder is applied in rubber production, a new way is provided for its recycling.
Description
Technical field
The invention belongs to utilization of the recycling of renewable resources technical field, more particularly to a kind of discarded printed circuit boards non-metal powder
Surface grafting polystyrene hybrid particle enhances butadiene-styrene rubber and preparation method thereof.
Background technology
Currently, with the high speed development of social economy, each electronic product become increasingly popular and update speed
Accelerate so that demand of the people to various electric equipment products increasingly improves.Printing electricity as " mother of electronic system product "
Road plate (PCB) is the basis of electronics industry, is primarily used to the interconnect of electronic component connection, such as by the various elements of fit on
Resistance, capacitance, semiconductor integrated chip, to as with certain function electronic unit, be widely used in mainframe computer,
In the various electronic equipments such as office and PC, household electrical appliance, entertainment electronic appliances and its supplementary prod.
But with the raising that the high precision of electronic and electrical equipment requires, cause to produce in printed circuit board production process
A large amount of unqualified useless circuit board, annual resulting discarded printed circuit boards quantity also increase sharply.Meanwhile with electronics
Model change frequency is accelerated and household electrical appliances are gone to the countryside, and the implementation of the policies such as old for new service, the quantity of waste electrical equipment is increasingly incremental,
The quantity of discarded printed circuit boards also increases therewith, it has also become increases after domestic waste and industrial refuse most fast and difficult
The solid waste of processing.
Under normal circumstances, the tenor in discarded printed circuit boards is 15%~30%, and Non-metallic components content is
70%~85%, organic substance and inorganic component about account for 40% and 60% respectively in nonmetallic materials.Organic matter be usually resin,
Brominated flame retardant, dicy-curing agent, curing accelerator etc.；Inorganic matter is typically with SiO2、CaO、Al2O3Based on it is a variety of
Glass fibre made of oxide.The wherein recovery and utilization technology of metal material comparative maturity, but for extracting valuable metal
Remaining nonmetallic materials afterwards, are often abandoned as rubbish, and not only resulting in waste of resources also increases environmental pressure.Therefore, how
Reasonably recycling nonmetal materials of discarded printed circuit boards becomes urgent problem to be solved.
Burning method, method of chemical treatment and object are mainly used to the recycling of nonmetal materials of discarded printed circuit boards at present
Recycling method is managed, but secondary pollution will produce to environment in view of burning method and method of chemical treatment, often by discarded printed circuit boards
Middle non-metallic part carries out physical crushing, and gained non-metal powder is added to as filler in other matrixes, to reduce composite wood
Expect cost, and improves Some Mechanical Properties.But as other fillers, the application of useless circuit board non-metal powder in the polymer,
There are problems that effectively dispersion and compatibility, at present frequently with addition compatilizer or using various coupling agents to discarded printed circuit
Plate non-metal powder surface carry out simple process come improve non-metal powder dispersibility and both compatibility, it is similar by discarded print
Printed circuit board non-metal powder prepares composite material as filler and has more report, but research focuses mostly in thermoplasticity and thermosetting property
Plastics it is filling-modified, and by discarded printed circuit boards non-metal powder by surface grafting polymerization reaction be prepared into hybrid particle after
It is filled into butadiene-styrene rubber, reduces the agglomeration of discarded printed circuit boards non-metal powder, and effectively promote the two compatibility, from
And it effectively improves butadiene-styrene rubber mechanical strength there is not been reported.
Invention content
The purpose of the present invention is be directed to discarded printed circuit boards non-metal powder in the prior art to enhance butylbenzene as filler
The problem of bad dispersibility present in rubber, easily reunion and poor compatibility, provide a kind of discarded printed circuit boards non-metal powder table
Face grafted polystyrene hybrid particle enhances butadiene-styrene rubber, and provides the preparation method of above-mentioned material, is reasonably utilizing useless print
While printed circuit board non-metal powder, its potential Resource Properties is taken full advantage of, there is preferable economy and social effect.
To achieve the goals above, the present invention uses following technical scheme：A kind of discarded printed circuit boards non-metal powder table
Face grafted polystyrene hybrid particle enhances butadiene-styrene rubber, includes the component of following mass fraction：100 parts of butadiene-styrene rubber is discarded
5~60 parts of printed circuit board non-metal powder surface grafting polystyrene hybrid particle, 2~10 parts of zinc oxide, 1~5 part of stearic acid,
1~5 part of anti-aging agent, 1~5 part of vulcanizing agent, 0.5~5 part of vulcanization accelerator.
Further, anti-aging agent is antioxidant A W, anti-aging agent RD, antioxidant A, antioxidant D, antioxidant 4010, anti-aging agent
At least one of DPPD, antioxidant D NP, antioxidant MB or antioxidant NBC.
Further, vulcanizing agent is sulphur, metal oxide, resin curing agent, sulfur donor, peroxide or polynary
At least one of amine.
Further, vulcanization accelerator is Vulcanization accelerator TMTD, accelerating agent TT, captax, altax, accelerant CZ, rush
Into at least one of agent AZ or accelerator DZ.
A kind of preparation of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing butadiene-styrene rubber
Method includes the following steps：
(1) refinement sieving：Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement, after refinement
Non-metal powder is spare after the sieving of 200 mesh standard sieves；
(2) surface acid activation process：Discarded printed circuit boards non-metal powder after refinement is sieved is placed in enough hydrochloric acid
In solution, the agitating and heating 6h at 70 DEG C, product is through filtering and being washed with distilled water for several times until neutral, and vacuum is dry at 80 DEG C
After dry 6h attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards non-metal powder；
(3) discarded printed circuit boards non-metal powder surface grafting gamma-aminopropyl-triethoxy-silane：At the acid activation of surface
The discarded printed circuit boards non-metal powder of reason is dispersed in dimethylbenzene, and after ultrasonic vibration 1h, dispersion liquid is moved into four-hole boiling flask,
Gamma-aminopropyl-triethoxy-silane is added into solution, then heat up high-speed stirred back flow reaction 16h, and product uses nothing after filtering
Water-ethanol washs repeatedly removes unreacted gamma-aminopropyl-triethoxy-silane, and crushes and grind after vacuum drying 6h at 50 DEG C
It grinds and is sieved through 200 mesh standard sieves and be grafted to get modified particle discarded printed circuit boards non-metal powder of the surface with primary amino group
Gamma-aminopropyl-triethoxy-silane；
(4) by modified discarded printed circuit boards non-metal powder grafting gamma-aminopropyl-triethoxy-silane and monomer benzene second
Alkene is added in four-hole boiling flask, and four-hole boiling flask is placed under mechanical agitator by ultrasonic vibration 5min, and distilled water, and logical nitrogen is added
30min is slowly ramped to 65 DEG C with the oxygen in exclusion system, and initiator ammonium persulfate is added, and constant temperature stirring 16h is grafted
Polymerisation, after reaction solids detached by ultracentrifugation, be used in combination tetrahydrofuran washing for several times, last graft product
It is dried in vacuo at 50 DEG C and obtains discarded printed circuit boards non-metal powder grafted polystyrene hybrid particle for 24 hours；
(5) with the hybrid particle modified enhancing butadiene-styrene rubber of discarded printed circuit boards non-metal powder grafted polystyrene obtained
Obtain enhancing butadiene-styrene rubber.
Further, the rotating speed of ball mill is 400~500r/min, 1~1.5h of Ball-milling Time in step 1.
Further, the molar concentration of hydrochloric acid solution is 1mol/L, discarded printed circuit boards non-metal powder and salt in step 2
The weight ratio of acid solution is 1:50.
Further, dimethylbenzene in step 3：The discarded printed circuit boards non-metal powder of surface acid activation process：γ-ammonia third
The weight ratio of ethyl triethoxy silicane alkane is 40:1：2.
Further, modified particle discarded printed circuit boards non-metal powder is grafted gamma-aminopropyl-triethoxy silicon in step 4
Alkane：Monomer styrene：Distilled water：The weight ratio of initiator is 1：20：300：0.2.
Further, step 5 specifically uses following steps：
(1) by butadiene-styrene rubber thin logical 10 plasticizings on a mill；
(2) zinc oxide, stearic acid, anti-aging agent, discarded printed circuit boards non-metal powder surface grafting polyphenyl second are sequentially added
Alkene hybrid particle, vulcanization accelerator, vulcanizing agent make a call to 3 triangle bags after being kneaded uniformly, adjust the uniform slice of wide roll spacing；
(3) rubber compound after mixing slice is placed on sulfidization molding on vulcanizing press and obtains the non-gold of discarded printed circuit boards
Belonging to powder surface grafting polystyrene hybrid particle enhances styrene-butadiene rubber, and curing temperature is 135~185 DEG C, vulcanization time 5
~120min, sulfide stress are 5~20MPa.
The present invention is refined first to discarded printed circuit boards non-metal powder and surface acid activation process, is drawn using surface
Graft polymerization procedure is sent out, the de- of gamma-aminopropyl-triethoxy-silane and discarded printed circuit boards non-metal powder surface hydroxyl is utilized
Alcohol reaction introduces primary amino group on its surface, then constitutes oxidation-reduction trigger system with ammonium persulfate, causes styrene in discarded print
Useless circuit board non-metal powder grafted polystyrene hybrid particle is made in the graft polymerization on printed circuit board non-metal powder surface；It will give up
Abandon printed circuit board non-metal powder grafted polystyrene hybrid particle, butadiene-styrene rubber, zinc oxide, stearic acid, anti-aging agent, vulcanization
After rubber compound is made in proportion in agent, vulcanization accelerator and other auxiliary agents, butadiene-styrene rubber product is made in final vulcanization.
Compared with the prior art, the present invention has the following advantages：
(1) present invention in discarded printed circuit boards non-metal powder surface grafting gamma-aminopropyl-triethoxy-silane by drawing
Enter amino, oxidation-reduction system is constituted with ammonium persulfate, styrene is realized in discarded printing using surface grafting polymerization reaction
Circuit board non-metal powder surface-active is graft-polymerized, and the discarded printed circuit boards non-metal powder surface grafting of high grafting rate has been made
Polystyrene hybrid particle.
(2) the discarded printed circuit boards non-metal powder that uses of present invention hybrid particle obtained after organic-treating has
Effect improves the compatibility of discarded printed circuit boards non-metal powder and butadiene-styrene rubber, and effectively increases it in butadiene-styrene rubber
Dispersibility, while vulcanization when can react with butadiene-styrene rubber macromolecular, formed chemical bonds, improve discarded printing
The binding force of circuit board non-metal powder and rubber.
(3) present invention is filled out using discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle as filler
Butadiene-styrene rubber is filled, the mechanical property of butadiene-styrene rubber can be not only effectively improved, and is the recycling of useless circuit board nonmetallic materials profit
With providing a new way.
Specific implementation mode
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiment.
Embodiment 1
Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement 1h, the non-metal powder warp after refinement
200 mesh standard sieves are sieved, and the discarded printed circuit boards non-metal powder after refinement is sieved is with hydrochloric acid solution according to weight ratio 1:50
Be placed in 1mol/L hydrochloric acid solutions, the agitating and heating 6h at 70 DEG C, product through filtering and being washed with distilled water for several times until neutral,
At 80 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards
Non-metal powder.
By the discarded printed circuit boards non-metal powder of surface acid activation process and dimethylbenzene according to weight ratio 1:40 are dispersed in
In dimethylbenzene, after ultrasonic vibration 1h, dispersion liquid is moved into four-hole boiling flask, according to acid activation discarded printed circuit boards non-metal powder
With gamma-aminopropyl-triethoxy-silane weight ratio 1:Gamma-aminopropyl-triethoxy-silane is added into solution for 2 ratio, then
Heat up high-speed stirred back flow reaction 16h, and product is washed after filtering with absolute ethyl alcohol and removes unreacted three second of γ-aminopropyl repeatedly
Oxysilane, and at 50 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves be sieved to get surface carry primary amino group
Modified particle discarded printed circuit boards non-metal powder be grafted gamma-aminopropyl-triethoxy-silane.
Modified discarded printed circuit boards non-metal powder grafting gamma-aminopropyl-triethoxy-silane is pressed with monomer styrene
According to weight ratio 1:20 are added in four-hole boiling flask, and four-hole boiling flask is placed under mechanical agitator, according to styrene by ultrasonic vibration 5min
With distilled water weight ratio 1:15 are added appropriate distilled water, and logical nitrogen 30min is slowly ramped to 65 with the oxygen in exclusion system
DEG C, according to styrene and ammonium persulfate weight ratio 100:1 is added appropriate initiator ammonium persulfate, and constant temperature stirring 16h is grafted
Polymerisation, after reaction solids detached by ultracentrifugation, be used in combination tetrahydrofuran washing for several times, last graft product
It is dried in vacuo at 50 DEG C and obtains discarded printed circuit boards non-metal powder grafted polystyrene hybrid particle for 24 hours.
By thin logical 10 plasticizings on a mill of 100 parts of butadiene-styrene rubber, 5 parts of zinc oxide, stearic acid 1 are then sequentially added
Part, 3 parts of antioxidant A, 15 parts of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle, 1 part of altax,
1.5 parts of sulphur makes a call to 3 triangle bags after being kneaded uniformly, adjust the uniform slice of wide roll spacing；Rubber compound after mixing slice is placed on tablet
Sulfidization molding obtains discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing butylbenzene rubber on vulcanizer
Glue material, curing temperature are 150 DEG C, vulcanization time 30min, sulfide stress 10MPa.
Discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle prepared by this technique enhances butylbenzene rubber
The tensile strength 3.92MPa of glue material, 100% stretching strength 0.81MPa, 300% stretching strength 1.38MPa, elongation at break
1168%, hardness 54.
Embodiment 2
Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement 1h, the non-metal powder warp after refinement
200 mesh standard sieves are sieved, and the discarded printed circuit boards non-metal powder after refinement is sieved is with hydrochloric acid solution according to weight ratio 1:50
Be placed in 1mol/L hydrochloric acid solutions, the agitating and heating 6h at 70 DEG C, product through filtering and being washed with distilled water for several times until neutral,
At 80 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards
Non-metal powder.
By the discarded printed circuit boards non-metal powder of surface acid activation process and dimethylbenzene according to weight ratio 1:40 are dispersed in
In dimethylbenzene, after ultrasonic vibration 1h, good general's dispersion liquid moves into four-hole boiling flask, nonmetallic according to acid activation discarded printed circuit boards
Powder and gamma-aminopropyl-triethoxy-silane weight ratio 1:Gamma-aminopropyl-triethoxy-silane is added into solution for 2 ratio, so
Heat up high-speed stirred back flow reaction 16h afterwards, and product is washed after filtering with absolute ethyl alcohol and removes unreacted γ-aminopropyl three repeatedly
Ethoxysilane, and at 50 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves be sieved to get surface carry primaquine
The modified particle waste printed circuit board nonmetal powder of base is grafted gamma-aminopropyl-triethoxy-silane.
By modified waste printed circuit board nonmetal powder grafting gamma-aminopropyl-triethoxy-silane and monomer styrene according to
Weight ratio 1:20 be added four-hole boiling flasks in, four-hole boiling flask is placed under mechanical agitator by ultrasonic vibration 5min, according to styrene with
Distilled water weight ratio 1:15 are added appropriate distilled water, and logical nitrogen 30min is slowly ramped to 65 with the oxygen in exclusion system
DEG C, according to styrene and ammonium persulfate weight ratio 100:1 is added appropriate initiator ammonium persulfate, and constant temperature stirring 16h is grafted
Polymerisation, after reaction solids detached by ultracentrifugation, be used in combination tetrahydrofuran washing for several times, last graft product
It is dried in vacuo at 50 DEG C and obtains waste printed circuit board nonmetal powder grafted polystyrene hybrid particle for 24 hours.
By thin logical 10 plasticizings on a mill of 100 parts of butadiene-styrene rubber, 5 parts of zinc oxide, stearic acid 2 are then sequentially added
Part, 2 parts of anti-aging agent RD, 30 parts of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle, accelerant CZ 1.5
Part, 2 parts of sulphur make a call to 3 triangle bags after being kneaded uniformly, adjust the uniform slice of width roll spacing；Rubber compound after mixing slice is placed on flat
Sulfidization molding obtains discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing butylbenzene on plate vulcanizer
Rubber material, curing temperature are 165 DEG C, vulcanization time 20min, sulfide stress 15MPa.
Discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle prepared by this technique enhances butylbenzene rubber
The tensile strength 8.32MPa of glue material, 100% stretching strength 1.58MPa, 300% stretching strength 2.85MPa, elongation at break
1328%, hardness 65.
Embodiment 3
Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement 1h, the non-metal powder warp after refinement
200 mesh standard sieves are sieved, and the discarded printed circuit boards non-metal powder after refinement is sieved is with hydrochloric acid solution according to weight ratio 1:50
Be placed in 1mol/L hydrochloric acid solutions, the agitating and heating 6h at 70 DEG C, product through filtering and being washed with distilled water for several times until neutral,
At 80 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards
Non-metal powder.
By the discarded printed circuit boards non-metal powder of surface acid activation process and dimethylbenzene according to weight ratio 1:40 are dispersed in
In dimethylbenzene, after ultrasonic vibration 1h, good general's dispersion liquid moves into four-hole boiling flask, nonmetallic according to acid activation discarded printed circuit boards
Powder and gamma-aminopropyl-triethoxy-silane weight ratio 1:Gamma-aminopropyl-triethoxy-silane is added into solution for 2 ratio, so
Heat up high-speed stirred back flow reaction 16h afterwards, and product is washed after filtering with absolute ethyl alcohol and removes unreacted γ-aminopropyl three repeatedly
Ethoxysilane, and at 50 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves be sieved to get surface carry primaquine
The modified particle waste printed circuit board nonmetal powder grafting gamma-aminopropyl-triethoxy-silane (useless PCB powder-APTES) of base.
By modified waste printed circuit board nonmetal powder grafting gamma-aminopropyl-triethoxy-silane and monomer styrene according to
Weight ratio 1:20 be added four-hole boiling flasks in, four-hole boiling flask is placed under mechanical agitator by ultrasonic vibration 5min, according to styrene with
Distilled water weight ratio 1:15 are added appropriate distilled water, and logical nitrogen 30min is slowly ramped to 65 with the oxygen in exclusion system
DEG C, according to styrene and ammonium persulfate weight ratio 100:1 is added appropriate initiator ammonium persulfate, and constant temperature stirring 16h is grafted
Polymerisation, after reaction solids detached by ultracentrifugation, be used in combination tetrahydrofuran washing for several times, last graft product
It is dried in vacuo at 50 DEG C and obtains waste printed circuit board nonmetal powder grafted polystyrene hybrid particle for 24 hours.
By thin logical 10 plasticizings on a mill of 100 parts of butadiene-styrene rubber, 3 parts of zinc oxide, stearic acid 1.5 are then sequentially added
Part, 5 parts of antioxidant MB, 40 parts of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle, accelerating agent
DM1.2 parts, 1.5 parts of captax, 0.5 part of sulphur make a call to 3 triangle bags after being kneaded uniformly, adjust the uniform slice of wide roll spacing；It will be kneaded
Rubber compound after slice is placed on sulfidization molding on vulcanizing press and obtains discarded printed circuit boards non-metal powder surface grafting polyphenyl
Ethylene hybrid particle enhances styrene-butadiene rubber, and curing temperature is 170 DEG C, vulcanization time 20min, sulfide stress 10MPa.
Discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle prepared by this technique enhances butylbenzene rubber
The tensile strength 10.61MPa of glue material, 100% stretching strength 2.32MPa, 300% stretching strength 3.55MPa, elongation at break
1178%, hardness 71.
Embodiment 4
Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement 1h, the non-metal powder warp after refinement
200 mesh standard sieves are sieved, and the discarded printed circuit boards non-metal powder after refinement is sieved is with hydrochloric acid solution according to weight ratio 1:50
Be placed in 1mol/L hydrochloric acid solutions, the agitating and heating 6h at 70 DEG C, product through filtering and being washed with distilled water for several times until neutral,
At 80 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards
Non-metal powder.
By the discarded printed circuit boards non-metal powder of surface acid activation process and dimethylbenzene according to weight ratio 1:40 are dispersed in
In dimethylbenzene, after ultrasonic vibration 1h, good general's dispersion liquid moves into four-hole boiling flask, nonmetallic according to acid activation discarded printed circuit boards
Powder and gamma-aminopropyl-triethoxy-silane weight ratio 1:Gamma-aminopropyl-triethoxy-silane is added into solution for 2 ratio, so
Heat up high-speed stirred back flow reaction 16h afterwards, and product is washed after filtering with absolute ethyl alcohol and removes unreacted γ-aminopropyl three repeatedly
Ethoxysilane, and at 50 DEG C be dried in vacuo 6h after attrition grinding and through 200 mesh standard sieves be sieved to get surface carry primaquine
The modified particle waste printed circuit board nonmetal powder of base is grafted gamma-aminopropyl-triethoxy-silane.
By modified waste printed circuit board nonmetal powder grafting gamma-aminopropyl-triethoxy-silane and monomer styrene according to
Weight ratio 1:20 be added four-hole boiling flasks in, four-hole boiling flask is placed under mechanical agitator by ultrasonic vibration 5min, according to styrene with
Distilled water weight ratio 1:15 are added appropriate distilled water, and logical nitrogen 30min is slowly ramped to 65 with the oxygen in exclusion system
DEG C, according to styrene and ammonium persulfate weight ratio 100:1 is added appropriate initiator ammonium persulfate, and constant temperature stirring 16h is grafted
Polymerisation, after reaction solids detached by ultracentrifugation, be used in combination tetrahydrofuran washing for several times, last graft product
It is dried in vacuo at 50 DEG C and obtains waste printed circuit board nonmetal powder grafted polystyrene hybrid particle for 24 hours.
By thin logical 10 plasticizings on a mill of 100 parts of butadiene-styrene rubber, 5 parts of zinc oxide, stearic acid 3 are then sequentially added
Part, 5 parts of antioxidant MB, 60 parts of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle, accelerant CZ 3
Part, 0.5 part of sulphur make a call to 3 triangle bags after being kneaded uniformly, adjust the uniform slice of width roll spacing；Rubber compound after mixing slice is placed on
Sulfidization molding obtains discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhancing fourth on vulcanizing press
Benzene rubber material, curing temperature are 155 DEG C, vulcanization time 30min, sulfide stress 15MPa.
Discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle prepared by this technique enhances butylbenzene rubber
The tensile strength 12.13MPa of glue material, 100% stretching strength 2.71MPa, 300% stretching strength 4.29MPa, elongation at break
1026%, hardness 79.
In order to better illustrate discarded printed circuit boards non-metal powder surface grafting polystyrene hydridization in instant component
The particle important function modified to butadiene-styrene rubber enhancing, comparative example 1-2, which has been investigated, does not carry out the discarded of surface grafting polymerization
Influence of the addition of printed circuit board non-metal powder to butadiene-styrene rubber mechanical property.
Comparative example 1
By thin logical 10 plasticizings on a mill of 100 parts of butadiene-styrene rubber, 5 parts of zinc oxide, stearic acid 1 are then sequentially added
Part, 3 parts of antioxidant A, 15 parts of unmodified discarded printed circuit boards non-metal powder, 1 part of altax, 1.5 parts of sulphur are kneaded uniform
After make a call to 3 triangle bags, adjust the uniform slice of wide roll spacing；Rubber compound after mixing slice is placed on sulfidization molding on vulcanizing press to obtain
Enhance styrene-butadiene rubber to discarded printed circuit boards non-metal powder, curing temperature is 150 DEG C, vulcanization time 30min, vulcanization
Pressure is 10MPa.
The tensile strength 2.38MPa of discarded printed circuit boards non-metal powder enhancing styrene-butadiene rubber prepared by this technique,
100% stretching strength 0.57MPa, 300% stretching strength 0.88MPa, elongation at break 868%, hardness 53.
Comparative example 2
By thin logical 10 plasticizings on a mill of 100 parts of butadiene-styrene rubber, 3 parts of zinc oxide, stearic acid 1.5 are then sequentially added
Part, 5 parts of antioxidant MB, 40 parts of discarded printed circuit boards non-metal powder, 1.2 parts of altax, 1.5 parts of captax, sulphur 0.5
Part, 3 triangle bags are made a call to after being kneaded uniformly, adjust the uniform slice of wide roll spacing；Rubber compound after mixing slice is placed on vulcanizing press
Upper sulfidization molding obtains discarded printed circuit boards non-metal powder enhancing styrene-butadiene rubber, and curing temperature is 170 DEG C, vulcanization time
For 20min, sulfide stress 10MPa.
The tensile strength 4.08MPa of discarded printed circuit boards non-metal powder enhancing styrene-butadiene rubber prepared by this technique,
100% stretching strength 1.24MPa, 300% stretching strength 1.73MPa, elongation at break 815%, hardness 68.
The above described is only a preferred embodiment of the present invention, not doing any type of limitation to the present invention.It is every
Technology and methods essence according to the present invention is to any simple modification, equivalent change and modification made by above example, still
Belong in the range of the technology and methods scheme of the present invention.
Claims (7)
1. a kind of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle enhances butadiene-styrene rubber, feature exists
In the component for including following mass fraction：100 parts of butadiene-styrene rubber, discarded printed circuit boards non-metal powder surface grafting polystyrene
5~60 parts of hybrid particle, 2~10 parts of zinc oxide, 1~5 part of stearic acid, 1~5 part of anti-aging agent, 1~5 part of vulcanizing agent, vulcanization promote
0.5~5 part of agent；
The anti-aging agent is antioxidant A W, anti-aging agent RD, antioxidant A, antioxidant D, antioxidant 4010, antioxidant DPPD, prevents always
At least one of agent DNP, antioxidant MB or antioxidant NBC；
The vulcanizing agent be sulphur, metal oxide, resin curing agent, sulfur donor, peroxide or polyamine in extremely
Few one kind；
The vulcanization accelerator is Vulcanization accelerator TMTD, captax, altax, accelerant CZ, accelerant A Z or accelerator DZ
At least one of；
The enhancing butadiene-styrene rubber is prepared using following steps：
(1) refinement sieving：Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement, the non-gold after refinement
It is spare after the sieving of 200 mesh standard sieves to belong to powder；
(2) surface acid activation process：Discarded printed circuit boards non-metal powder after refinement is sieved is placed in enough hydrochloric acid solutions
In, the agitating and heating 6h at 70 DEG C, product is through filtering and being washed with distilled water for several times until neutrality, 6h is dried in vacuo at 80 DEG C
Afterwards attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards non-metal powder；
(3) discarded printed circuit boards non-metal powder surface grafting gamma-aminopropyl-triethoxy-silane：By surface acid activation process
Discarded printed circuit boards non-metal powder is dispersed in dimethylbenzene, after ultrasonic vibration 1h, dispersion liquid is moved into four-hole boiling flask, Xiang Rong
Gamma-aminopropyl-triethoxy-silane is added in liquid, then heat up high-speed stirred back flow reaction 16h, with anhydrous second after product suction filtration
Alcohol washs repeatedly removes unreacted gamma-aminopropyl-triethoxy-silane, and attrition grinding is simultaneously after being dried in vacuo 6h at 50 DEG C
It is sieved through 200 mesh standard sieves and is grafted γ-ammonia to get modified particle discarded printed circuit boards non-metal powder of the surface with primary amino group
Propyl-triethoxysilicane；
(4) modified discarded printed circuit boards non-metal powder grafting gamma-aminopropyl-triethoxy-silane and monomer styrene are added
Enter in four-hole boiling flask, four-hole boiling flask is placed under mechanical agitator by ultrasonic vibration 5min, and distilled water, and logical nitrogen 30min is added
With the oxygen in exclusion system, 65 DEG C are slowly ramped to, initiator ammonium persulfate is added, constant temperature stirring 16h is graft-polymerized
Reaction, solids are detached by ultracentrifugation after reaction, tetrahydrofuran washing are used in combination for several times, last graft product is 50
It is dried in vacuo at DEG C and obtains discarded printed circuit boards non-metal powder grafted polystyrene hybrid particle for 24 hours；
(5) it is obtained with the hybrid particle modified enhancing butadiene-styrene rubber of discarded printed circuit boards non-metal powder grafted polystyrene obtained
Enhance butadiene-styrene rubber.
2. a kind of discarded printed circuit boards non-metal powder surface grafting polystyrene hybrid particle according to claim 1 increases
The preparation method of strong butadiene-styrene rubber, it is characterised in that include the following steps：
(1) refinement sieving：Discarded printed circuit boards non-metal powder is added in ball mill and is ground refinement, the non-gold after refinement
It is spare after the sieving of 200 mesh standard sieves to belong to powder；
(2) surface acid activation process：Discarded printed circuit boards non-metal powder after refinement is sieved is placed in enough hydrochloric acid solutions
In, the agitating and heating 6h at 70 DEG C, product is through filtering and being washed with distilled water for several times until neutrality, 6h is dried in vacuo at 80 DEG C
Afterwards attrition grinding and through 200 mesh standard sieves sieving after obtain surface acid activation discarded printed circuit boards non-metal powder；
(3) discarded printed circuit boards non-metal powder surface grafting gamma-aminopropyl-triethoxy-silane：By surface acid activation process
Discarded printed circuit boards non-metal powder is dispersed in dimethylbenzene, after ultrasonic vibration 1h, dispersion liquid is moved into four-hole boiling flask, Xiang Rong
Gamma-aminopropyl-triethoxy-silane is added in liquid, then heat up high-speed stirred back flow reaction 16h, with anhydrous second after product suction filtration
Alcohol washs repeatedly removes unreacted gamma-aminopropyl-triethoxy-silane, and attrition grinding is simultaneously after being dried in vacuo 6h at 50 DEG C
It is sieved through 200 mesh standard sieves and is grafted γ-ammonia to get modified particle discarded printed circuit boards non-metal powder of the surface with primary amino group
Propyl-triethoxysilicane；
(4) modified discarded printed circuit boards non-metal powder grafting gamma-aminopropyl-triethoxy-silane and monomer styrene are added
Enter in four-hole boiling flask, four-hole boiling flask is placed under mechanical agitator by ultrasonic vibration 5min, and distilled water, and logical nitrogen 30min is added
With the oxygen in exclusion system, 65 DEG C are slowly ramped to, initiator ammonium persulfate is added, constant temperature stirring 16h is graft-polymerized
Reaction, solids are detached by ultracentrifugation after reaction, tetrahydrofuran washing are used in combination for several times, last graft product is 50
It is dried in vacuo at DEG C and obtains discarded printed circuit boards non-metal powder grafted polystyrene hybrid particle for 24 hours；
(5) it is obtained with the hybrid particle modified enhancing butadiene-styrene rubber of discarded printed circuit boards non-metal powder grafted polystyrene obtained
Enhance butadiene-styrene rubber.
3. preparation method according to claim 2, it is characterised in that：In the step 1 rotating speed of ball mill be 400~
500r/min, 1~1.5h of Ball-milling Time.
4. preparation method according to claim 2, it is characterised in that：The molar concentration of hydrochloric acid solution is in the step 2
The weight ratio of 1mol/L, discarded printed circuit boards non-metal powder and hydrochloric acid solution is 1:50.
5. preparation method according to claim 2, it is characterised in that：Dimethylbenzene in the step 3：Surface acid activation process
Discarded printed circuit boards non-metal powder：The weight ratio of gamma-aminopropyl-triethoxy-silane is 40：1：2.
6. preparation method according to claim 2, it is characterised in that：Modified particle discarded printed circuit in the step 4
Plate non-metal powder is grafted gamma-aminopropyl-triethoxy-silane：Monomer styrene：Distilled water：The weight ratio of initiator is 1：20：
300：0.2.
7. preparation method according to claim 2, it is characterised in that：The step 5 specifically uses following steps：
(1) by butadiene-styrene rubber thin logical 10 plasticizings on a mill；
(2) it is miscellaneous that zinc oxide, stearic acid, anti-aging agent, discarded printed circuit boards non-metal powder surface grafting polystyrene are sequentially added
Change particle, vulcanization accelerator, vulcanizing agent, 3 triangle bags are made a call to after being kneaded uniformly, adjusts the uniform slice of wide roll spacing；
(3) rubber compound after mixing slice is placed on sulfidization molding on vulcanizing press and obtains discarded printed circuit boards non-metal powder
Surface grafting polystyrene hybrid particle enhance styrene-butadiene rubber, curing temperature be 135~185 DEG C, vulcanization time be 5~
120min, sulfide stress are 5~20MPa.
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| CN107722395B (en) * | 2017-09-30 | 2020-09-22 | 华南理工大学 | Hyperbranched modified waste printed circuit board nonmetal powder hybrid filler and preparation method and application thereof |
| CN109103764A (en) * | 2018-06-10 | 2018-12-28 | 江苏中讯电力科技有限公司 | A kind of low pressure high-performance intelligent switchboard |
| RU2686035C1 (en) * | 2018-06-22 | 2019-04-23 | Федеральное государственное автономное образовательное учреждение высшего образования "Северо-Восточный федеральный университет имени М.К.Аммосова" | Rubber mixture based on butadiene-styrene rubber with schungite |
| CN110305380B (en) * | 2019-07-10 | 2021-09-21 | 华南理工大学 | Rubber compound based on waste printed circuit board nonmetal powder and preparation method thereof |
| CN110669268A (en) * | 2019-10-09 | 2020-01-10 | 芜湖风雪橡胶有限公司 | Reinforced styrene butadiene rubber and preparation method thereof |
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