CN105694239B - A kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material and preparation method thereof - Google Patents
A kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material and preparation method thereof Download PDFInfo
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- CN105694239B CN105694239B CN201610242371.XA CN201610242371A CN105694239B CN 105694239 B CN105694239 B CN 105694239B CN 201610242371 A CN201610242371 A CN 201610242371A CN 105694239 B CN105694239 B CN 105694239B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
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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
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Abstract
The invention discloses a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material and preparation method thereof, the composite is made up of the raw material of following parts by weight：100 parts of ethylene propylene diene rubber；Modified 20~120 parts of printed circuit board (PCB) non-metal powder；It is grafted 5~15 parts of ethylene propylene diene rubber；0~80 part of plasticizer；0~50 part of filler；2~5 parts of accelerator；3~5 parts of zinc oxide；0.8~1.2 part of stearic acid；0.5~1.5 part of sulphur.The present invention has reclaimed the non-metal powder in waste printed circuit board, improves reinforcement ability of the discarded printed circuit boards non-metal powder in ethylene propylene diene rubber so that waste printed circuit board nonmetal powder can be effective as the reinforced filling of ethylene propylene diene rubber.The application of discarded printed circuit boards non-metal powder from plastics are generalized to rubber, is conducive to environmental protection by the present invention.
Description
Technical field
The invention mainly relates to electronic product recycling recycling field, the recovery on discarded printed circuit boards non-metal powder
Utilize, more particularly to a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material and preparation method thereof.
Background technology
With the implementation of China's strategy of sustainable development, higher requirement, time of electronic waste are proposed to environmental protection
Receive with utilizing the thorny problem faced as majority state.Current China turns into the production and consumption big country of household electrical appliance, only
2% calculating is updated to scrap in year, 4 superseded major class household electrical appliance add what popularization in the whole society was used just up to 20,000,000 every year
Update cycle only has the high-tech electronic product such as 2-4 computer, mobile phone, and the novel household appliance of high quality and at a reasonable price continued to bring out
Product so that the renewal of scrapping in actual year of China's household electrical appliance is up to more than 25,000,000.Printed circuit board (PCB)（PCB）As useless
The critical component abandoned in household electrical appliances, it is reclaimed and recycling problem turns into the hot issue for being badly in need of solving.At present China into
For the big producing countries of PCB first, a large amount of leftover pieces, the recovery of useless plate in production process also face great difficult problem.
The value of metal is always discarded printed circuit boards（WPCBs）The direct driving force of recovery.By the gold of sorting enrichment
Category can typically be sent to metal smelt company and carry out deep processing or electrorefining.And account for the glass fibers of board quality 70% or so
Tie up toner（That is non-metal powder）Due to complicated component and relatively low recovery value, the Resource analysis for it is caused
It is fewer, it is estimated that China is annual will to produce 150,000 tons of WPCBs non-metal powders.At present, China is to same with thermosetting compound material
The processing of discarded object is mainly taken landfill and burned.In principle, landfill disposal selection is taken in gully or wasteland, also some units
Bury nearby, this method can cause the destruction of soil and the waste in a large amount of soils.Burning disposal, which is typically used, directly burns, this
The method of kind is fairly simple, does not result in land wastage, but due to producing a large amount of poison gases in burning, can cause environmental pollution.
In industrially developed country, particularly in Europe, same with thermosetting compound material recovery and utilization technology is increasingly concerned by people.Respectively
Relevant major company's joint investment, combine and found the factory, and have government-funded.Reclaim processing factory it is many using crush and be pyrolyzed law technology as
It is main, possess certain scale, technology reaches its maturity, its main direction of studying is roughly divided into 2 aspects, one is that research is non-renewable
The processing new technology of same with thermosetting compound material discarded object, two be renewable, the degradable new material of exploitation.Recovery method has following
3 kinds of main methods, i.e. energy regenerating（Burning method）, chemical recovery（Pyrolysismethod）, particle reclaim（Comminuting method）.No matter can from technology
For row or practicality, crush absorption method be the most desirable, recyclable same with thermosetting compound material discarded object kind compared with
It is many, to the same with thermosetting compound material discarded object for being difficult to reclaim with conventional method（Such as PCB discarded objects）Also can preferably it reclaim, and not
Environment can be polluted, be an important development direction for solving same with thermosetting compound material waste pollution.Discarded circuit board
The main composition of substrate is fibre strengthening thermosetting resin, the characteristics of due to thermosetting plastics itself, and calorific value is reclaimed except burning
Outside, being also used as powder is used for the re-using such as coating, paveio(u)r；Although these regeneration quality are low, class is not high,
And be also irrational in terms of economic investment and the utilization of resources, still, result of study in recent years shows, thermosetting plastics
Composite can be made again, can carry out separating pulverization process, selection according to the differences of discarded circuit board substrate raw materials
New resin matrix, final production goes out a variety of composites, i.e. composite material of waste.
Physics completion method handles non-metal powder, and the chemical state without changing non-metal powder can be used as conventional packing and use,
Technical feasibility, pollution-free, treating capacity are big and are easy to industrial applications, are the technologies that non-metal powder recycling has preferable prospect.Mesh
Before, domestic and international researcher has also carried out the trial of some physics completion methods to WPCBs non-metal powders, and makes certain gains.Such as：
Document 1（Mou, P.; Xiang, D.; Duan, G. Products made from nonmetallic materials
reclaimed from wasteprinted circuit boards. Tsinghua Sci. Technol. 2007, 12
(3): 276-283.）；Document 2（Mou, P. New solutions for reusing nonmentals reclaimed
from waste printed circuit boards. Proceedings of the IEEE International
Symposium on Electronics and the Environment, IEEE: New York, 2005; pp 205-
209.）Reuse method to non-metal powder carries out a variety of attempt.By different processing methods, prepare a variety of nonmetallic
Powder packing material, such as fragment of brick, cloaca grid, composite board and mouse model.
Cement solidification technology is also used for WPCBs processing disposal, such as：Document 3（Niu, X. Treatment of
waste printed wire boards in electronic waste for safe disposal. J. Hazard.
Mater. 2007, 145 (3): 410-416.）Circuit board is solidified using two methods of high pressure compressed and cement solidification
Disposal.Document 4（Huang hair honor phenolic resin and its application Beijing, Chemical Industry Press, 2003.）Reporting will be broken, quiet
Resin-oatmeal obtained by electricity sorting copper foil base phenolic board adds 10% or so as papery phenolic laminated sheet filler, can be to some extent
Improve mobility and the mechanical electric apparatus performance of curing rate and product.
Some domestic scientific research personnel have also carried out filling to non-metal powder and recycled, and such as prepare poly- third by nonmetal powder filled
Alkene（PP）And polyvinyl chloride（PVC）Composite, such as：Document 5（Zheng, Y. The reuse of nonmetals
recycled from waste printed circuit boards as reinforcing fillers in the
polypropylene composites. J. Hazard. Mater. 2009, 163 (2-3): 600-606）, document 6
（Zheng, Y. A novel approach to recycling of glass fibers from nonmetal
materials of waste printed circuit boards. J. Hazard. Mater. 2009, 170 (2-3):
978-982.）, document 7（Linzhi's discarded circuit board epoxy resin reutilization technology pre-test environmental science and technology .2009,22（5）：
1-3.）.Some patent documents are directed to research in this respect, and such as CN101591459 A are prepared for the non-gold of waste printed circuit board
Belong to powder/acrylic resin composite；CN103087458 B are prepared for waste printed circuit board nonmetal powder/ABS resin composite wood
Material；CN101190981 B use polypropylene be matrix resin, ethylene propylene diene rubber as toughener, add waste printed circuit board
Material dedicated for bumper has been made in non-metal powder；CN101591459 B are with waste printed circuit board nonmetal powder, high-density polyethylene
Wood-plastic material has been made in alkene and wood powder；The B of CN 102161806 are with waste printed circuit board nonmetal powder, polyvinyl chloride, chlorinated polyethylene
Wood-plastic material has been made in alkene and wood powder；The B of CN 102161802 are prepared for waste printed circuit board nonmetal powder/polyvinyl chloride and are combined
Material；Waste printed circuit board nonmetal powder is used to reclaim polyacrylic filling-modified by the B of CN 102226025.
So far, waste printed circuit board nonmetal powder concentrates on thermoplasticity and thermosetting in the filling-modified of polymer
Plastics it is filling-modified in, nonmetallic reclaimed materials of modification printed circuit board (PCB) and preparation method thereof institute that the B of CN 102675717 are proposed
Obtained modified non-metal powder is also to be only applicable among filling plastic, and discarded printed circuit boards non-metal powder is applied in rubber
There is not been reported for filling-modified in material, and for present circumstances, discarded printed circuit boards non-metal powder is directly added into rubber
After glue, it can not play a part of reinforcement, can only be used as inert filler.If its reinforcing property in rubber can be improved,
Important meaning is respectively provided with to improving the added value for recycling material, the cost for economizing on resources, reducing product.
The content of the invention
The ethylene propylene diene rubber tool that the present invention can not to add discarded printed circuit boards non-metal powder for prior art
There is higher mechanical property and a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material is provided, carried with this
Reinforcing property of the high discarded printed circuit boards non-metal powder in ethylene propylene diene rubber.
Another object of the present invention is to provide a kind of discarded printed circuit boards non-metal powder/ethylene propylene diene rubber composite wood
The preparation method of material.
The present invention technical principle be：Discarded printed circuit boards non-metal powder is refined first and ozone activation at
Reason, then pre-processed with mercaptosilane coupling agents；Afterwards by discarded printed circuit boards non-metal powder, the maleic anhydride of pretreatment
（Or unsaturated carboxylic acid）Be grafted ethylene propylene diene rubber, ethylene propylene diene rubber, plasticizer, filler, accelerator, zinc oxide, stearic acid,
Sulphur is made after elastomeric compound, and product is made in vulcanization.
The technical problems to be solved by the invention are solved by following scheme：A kind of discarded printed circuit boards are nonmetallic
Powder/ternary ethlene propyene rubbercompound material, the composite is made up of the raw material of following parts by weight：
100 parts of ethylene propylene diene rubber；
Modified 20~120 parts of printed circuit board (PCB) non-metal powder；
It is grafted 5~15 parts of ethylene propylene diene rubber；
0~80 part of plasticizer；
0~50 part of filler；
2~5 parts of accelerator；
3~5 parts of zinc oxide；
0.8~1.2 part of stearic acid；
0.5~1.5 part of sulphur.
It is preferred that, modified printed circuit board (PCB) non-metal powder of the present invention is made as follows：
1）Mercaptosilane coupling agents are dissolved in alcohol solvent, alcoholysis is stood, mercaptosilane coupling agents ethanol are made molten
Liquid；
2）Printed circuit board (PCB) non-metal powder after ball milling, sieving is placed in ozone and activated；
3）By step 2）Printed circuit board (PCB) non-metal powder after activation is placed in homogenizer and stirred, and adds while stirring
Step 1）Obtained coupling agent solution, spontaneously dries, is subsequently placed in oven for drying.
Wherein, step 1）In, the mass percentage concentration of mercaptosilane coupling agents ethanol solution is 10~50%, alcoholysis time
For 5~30 minutes；Step 2）In, soak time is 3~15 minutes；Step 3）In, homogenizer rotating speed is 500~1000
Rev/min, mixing time is 10~30 minutes, 80~120 DEG C of oven temperature, drying time 1~3 hour, the hydrosulphonyl silane
The consumption of coupling agent is the 0.5~1.5% of modified printed circuit board (PCB) non-metal powder quality, and the mercaptosilane coupling agents are mercapto third
Base trimethoxy silane or mercaptopropyltriethoxysilane.
It is further preferred that it is of the present invention grafting ethylene propylene diene rubber be selected from maleic anhydride, maleic acid, acrylic acid or
One kind in methacrylic acid grafting ethylene propylene diene rubber, described grafting ethylene propylene diene rubber gel content is less than 2%, grafting
Rate is 2~8%, and the grafting ethylene propylene diene rubber passes through sulphur by ethylene propylene diene rubber and grafted monomers under high temperature and high shear force
Alcohol-alkene reaction is made, and described grafted monomers have following general structure：
Wherein, R is selected from,OrIn one kind.
It is furthermore preferred that grafted monomers of the present invention can be made by following steps：
1）By the dissolving of mercaptopropionic acid pentaerythritol ester in organic solvent, it is made into the first solution；
2）Unsaturated carboxylic acid or acid anhydrides are dissolved in organic solvent, and add radical initiator, the second solution is made into；
3）The first solution is heated, the second solution is added dropwise while stirring, continues to react after completion of dropwise addition, is removed under reduced pressure organic molten
Agent, produces polyfunctional group grafted monomers；
Wherein, step 1）Described in the first solution mass percentage concentration be 20~60%, step 2）Described in the second solution
Mass percentage concentration be 20~60%, the addition of the radical initiator for mercaptopropionic acid pentaerythritol ester with it is unsaturated
The mol ratio of the 0.2~2% of carboxylic acid or acid anhydrides quality sum, mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid or acid anhydrides is 1：
3, step 3）Described in the first solution heating-up temperature be 60~90 DEG C, the reaction time be 0.5~2 hour；
The one kind of described organic solvent in toluene, acetone, ethyl acetate, described unsaturated carboxylic acid or acid anhydrides choosing
One kind from maleic anhydride, maleic acid, methacrylic acid or acrylic acid, described radical initiator is benzoyl peroxide
Formyl or azodiisobutyronitrile.
Particularly, grafted monomers of the present invention can also be made by following steps：
1）By the dissolving of mercaptopropionic acid pentaerythritol ester in organic solvent, it is made into the first solution；
2）By unsaturated carboxylic acid or acid anhydrides dissolving in organic solvent, light trigger is added, the second solution is made into；
3）At normal temperatures, the second solution is slowly added dropwise to the first solution while stirring, while side carries out ultraviolet lighting, drop
Plus after terminating, proceed ultraviolet lighting, removal of solvent under reduced pressure obtains polyfunctional group grafted monomers；
Wherein, step 1）Described in the first solution mass percentage concentration be 20~60%, step 2）Described in the second solution
Mass percentage concentration be 20~60%, the light trigger addition be mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid or
The mol ratio of the 0.2~2% of acid anhydrides quality sum, wherein mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid or acid anhydrides is 1：3,
Step 3）Middle time for adding is 30~60 minutes, and it is 10~30 minutes to continue the ultraviolet lighting time；
The one kind of described organic solvent in toluene, acetone, ethyl acetate, described unsaturated carboxylic acid or acid anhydrides choosing
One kind from maleic anhydride, maleic acid, methacrylic acid or acrylic acid, described light trigger is selected from light trigger
One kind in 184,1173,907,659.
One or more of the filler of the present invention in carbon black, white carbon, clay, calcium carbonate, talcum powder, the rush
Enter agent and be selected from accelerator PZ, accelerant B Z, captax, altax, Vulcanization accelerator TMTD, acceterator TE, accelerant CZ, promotion
One or more in agent CBS；Any one of described plasticizer in chlorinated paraffin, paraffin oil, naphthenic oil, aromatic naphtha
Or it is several.
Realize technical scheme that another object of the present invention used for：A kind of discarded printed circuit boards non-metal powder/ternary
The preparation method of EP rubbers composite, its specific preparation process is：
1）Dispensing：Ethylene propylene diene rubber, modified printed circuit board (PCB) non-metal powder, grafting EPDM are weighed by mass fraction
Rubber, plasticizer, filler, accelerator, zinc oxide, stearic acid, sulphur；
2）Mixing：By ethylene propylene diene rubber, modified printed circuit board (PCB) non-metal powder, grafting ethylene propylene diene rubber, plasticizer,
Filler, zinc oxide, stearic acid input banbury are kneaded, and melting temperature is 80~160 DEG C, and mixing time is 5~10 minutes；
It is cooled to after less than 60 DEG C, adds sulphur and accelerator, sizing material is made no more than 80 DEG C in banburying chamber's temperature control；
3）Vulcanization：By step 2）Prepared sizing material, is vulcanized after calendering, extrusion molding, discarded printing is made
Circuit board non-metal powder/ternary ethlene propyene rubbercompound material.
The present invention compared with prior art, has the following advantages that：
1）The present invention is equal to the glass fibre and the epoxy powder of solidification in discarded printed circuit boards non-metal powder
Activated, both of which can be combined by chemical bond with ethylene propylene diene rubber macromolecular, therefore greatly increase it
Reinforcing property, is mixed into after rubber as the modified abandoned printed circuit board (PCB) non-metal powder of reinforcing agent, can not only improve rubber
The mechanical property such as stress at definite elongation and tensile strength, but also cost can be reduced and improve processing performance.
2）The present invention carries out activation process using ozone to discarded printed circuit boards non-metal powder, to remove the one of its surface
Layer epoxy resin, and cause fiberglass surfacing to produce substantial amounts of silicone hydroxyl, so as to improve silane coupler and glass fibre
Reactivity.It is industrially conventional method to siliceous filler progress processing using silane coupler, for this area
Silane coupler processing directly can be carried out to discarded printed circuit boards non-metal powder using silane coupler for technical staff, so
And in the present invention, inventor has found：The main component of glass fibre in discarded printed circuit boards non-metal powder is silicate,
Seldom, and most surfaces can still be wrapped up by one layer of very thin epoxy resin when broken for the silicone hydroxyl on its surface, so directly
The effect for tapping into the processing of row silane coupler is poor.
3）With the silicone hydroxyl of fiberglass surfacing condensation reaction can occur for the mercaptosilane coupling agents that the present invention is selected, from
And sulfydryl in the fiberglass surfacing grafting in discarded printed circuit boards non-metal powder, sulfydryl can be with rubber in the vulcanization of rubber
Macromolecular reacts together, so as to chemical bonds, improve the adhesion of glass fibre and rubber.
4）Maleic anhydride that the present invention is selected, acrylic or methacrylic acid grafting ethylene propylene diene rubber, acid anhydrides therein
（Or carboxylic acid）With the epoxy resin in discarded printed circuit boards non-metal powder esterification can occur for group when high temperature vulcanized, this
It is, because epoxy resin is generally using amine as curing agent, to react to be consolidated by active hydrogen and the epoxide group of amino
Change, still there are a large amount of unreacted hydroxyls in the epoxy resin structural after solidification.Hydroxyl and maleic anhydride（Or maleic acid, propylene
Acid, methacrylic acid）It is grafted the acid anhydrides in ethylene propylene diene rubber（Or carboxylic acid）Esterification occurs when high temperature vulcanized for group, from
And combined with chemical bond with grafting ethylene propylene diene rubber, and be grafted ethylene propylene diene rubber still can occur with ethylene propylene diene rubber
Vulcanization reaction, forms three-dimensional net structure, so, and the epoxy resin after solidification divides greatly in vulcanization also by chemical bond with rubber
Son is combined together.
5）The application of discarded printed circuit boards non-metal powder from plastics are generalized to rubber, is conducive to environment to protect by the present invention
Shield.
Brief description of the drawings
Fig. 1 is the SEM figures of waste circuit board non-metal powder not treated by ozone.
Fig. 2 is the SEM figures of waste circuit board non-metal powder treated by ozone.
Embodiment
Concrete technical scheme of the invention described further below, in order to which those skilled in the art further understands this
Invention, without constituting the limitation to right.
Concrete technical scheme of the present invention is as follows：
1）The preparation of modified abandoned circuit board non-metal powder
Waste circuit board non-metal powder after ball milling 1~8 hour, is activated 3~15 in ball mill in ozone after sieving
Minute after, add mass percentage concentration for 10~50% alcoholysis mercaptosilane coupling agents ethanol solution in, the alcoholysis time be 5~
30 minutes, mixing time was 10~30 minutes, and speed of agitator is 500~1000 revs/min, is spontaneously dried；Place it in again
Dried 1~3 hour in 80~120 DEG C of baking ovens, obtain modified abandoned circuit board non-metal powder, wherein, described hydrosulphonyl silane coupling
The one kind or mixture of agent in mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane.Can from accompanying drawing 1 and accompanying drawing 2
See, after ozone processing, the epoxy resin of fiberglass surfacing has been removed.
2）Dispensing
100 parts of ethylene propylene diene rubber, modified 20~120 parts of printed circuit board (PCB) non-metal powder, grafting are weighed by mass fraction
5~15 parts of ethylene propylene diene rubber, 0~80 part of plasticizer, 0~50 part of filler, 2~5 parts of accelerator, 3~5 parts of zinc oxide, hard ester
Sour 0.8~1.2 part, 0.5~1.5 part of sulphur.
Wherein, described ethylene propylene diene rubber is commercially available business product, can be any trade mark, or two kinds and two or more boards
Number mixture；Described plasticizer is any one in chlorinated paraffin, paraffin oil, naphthenic oil and aromatic naphtha or its group
Close.
Described grafting ethylene propylene diene rubber is selected from maleic anhydride grafting ethylene propylene diene rubber, acrylic acid-grafted EPDM
One kind in rubber or methacrylic acid grafting ethylene propylene diene rubber, the gel content of grafting ethylene propylene diene rubber is less than 2%, connect
Branch rate is 2~8%, preferably 6~8%.The grafting ethylene propylene diene rubber is by ethylene propylene diene rubber and grafted monomers in high temperature and height
Reacted and be made by mercaptan-alkene under shearing force, described grafted monomers have following general structure：
Wherein, R is selected from,OrIn one kind.
3）Mixing
All raw materials input banbury in addition to sulphur and accelerator is kneaded, melting temperature is 80~160 DEG C,
Mixing time is 5~10 minutes.Above sizing material is cooled to after less than 60 DEG C, and sulphur and accelerator, banburying are added in banbury
Room temperature is controlled no more than 80 DEG C；Sulphur and accelerator also can on a mill add after sizing material is cooled to below 60 DEG C.
4）Vulcanization
Sizing material prepared by the present invention, can be vulcanized, sulphur after the traditional rubber processing method shaping such as calendering, extrusion
Change method can be carried out according to the difference of product with common various vulcanization process, such as molding vulcanization, sulfurizing pot vulcanization, be made each
Plant product.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
Waste circuit board non-metal powder after ball milling sieving in 1 hour, is activated 15 minutes in ozone, taken in ball mill
100 grams add 100 gram mass percentage concentrations to be stirred in 0.5% mercaptosilane coupling agents ethanol solution 30 minutes, do naturally
It is dry；Place it in 80 DEG C of baking ovens and dry 1 hour again, obtain modified abandoned circuit board non-metal powder.
Embodiment 2
Waste circuit board non-metal powder after ball milling sieving in 8 hours, is activated 3 minutes in ozone in ball mill, takes 100
Gram add 100 gram mass percentage concentrations be 1% mercaptosilane coupling agents ethanol solution in stir 10 minutes, spontaneously dry；Again by it
It is placed in 120 DEG C of baking ovens and dries 3 hours, obtains modified abandoned circuit board non-metal powder.
Embodiment 3
Waste circuit board non-metal powder after ball milling sieving in 4 hours, is activated 9 minutes in ozone in ball mill, takes 100
Gram add 100 gram mass percentage concentrations be 1.5% mercaptosilane coupling agents ethanol solution in stir 20 minutes, spontaneously dry；Again will
It, which is placed in 120 DEG C of baking ovens, dries 2 hours, obtains modified abandoned circuit board non-metal powder.
Embodiment 4
24.4 grams are added in 97.6 grams of acetone（0.05mol）Mercaptopropionic acid pentaerythritol ester, stirring and dissolving obtains first
Solution.14.7 grams are added in 58.8 grams of acetone（0.15mol）Maleic anhydride, 0.0782 gram of light trigger Irgacure 184,
1173rd, one kind in 907,659, stirring and dissolving obtains the second solution.First solution is added agitator, reflux condensation mode are housed
In 125 milliliters of three mouthfuls of quartz flasks of pipe, the second solution is added dropwise in side, while carrying out ultraviolet lighting, 10 minutes with 250W high-pressure sodium lamps
Drip off.Continue illumination 30 minutes after being added dropwise to complete, revolving removes acetone, obtains maleic anhydride grafted monomers product（Water white transparency
It is semi-solid）.
By obtained 3 grams of maleic anhydride grafted monomers, 40 grams of ethylene propylene diene rubbers（Mitsui company 4045M）Plus
In the banburying chamber for entering torque rheometer, rotor speed is 30 revs/min, and mixing chamber temperature is 200 DEG C, after kneading 15 minutes, is obtained
EPDM-g-MAH.Gel content is 0, and it is 6.7% that titration, which measures grafting rate,.
Embodiment 5
24.4 grams are added in 36.6 grams of toluene（0.05mol）Mercaptopropionic acid pentaerythritol ester, stirring and dissolving obtains first
Solution.12.9 grams are added in 36.6 grams of toluene（0.15mol）Methacrylic acid, 0.373 gram of benzoyl peroxide, are stirred molten
Solution, obtains the second solution.First solution is added and is equipped with agitator, 125 milliliters of three mouthfuls of glass flasks of reflux condensing tube, plus
Heat is added dropwise the second solution, dripped off within 1 hour while stirring to flowing back.Continue back flow reaction after being added dropwise to complete 1 hour, rotation is removed
Toluene, obtains methacrylic acid grafted monomers product（Water white transparency thick liquid）.
Take 160 grams of methacrylic acid grafted monomers, 5000 grams of ethylene propylene diene rubbers（LG-DOW Nordel IP4725)
After being mixed 15 minutes in high-speed mixer, add in parallel dual-screw extruding machine, extruder draw ratio is 1：24, body temperature is
220 DEG C, rotating speed is 50 revs/min, obtains EPDM-g-AA, gel content is 0, and it is 2.9% that titration, which measures grafting rate,.
Embodiment 6
Weigh ethylene propylene diene rubber（Mitsui, 4045M）100 parts, 5 parts of zinc oxide, 1 part of stearic acid, embodiment 1 is made
80 parts standby of modified abandoned circuit board non-metal powder, 1.2 parts of sulphur, 0.5 part of accelerant B Z, 1.0 parts of altax, accelerator
1.2 parts of CBS, after mixer mixing is uniform, compression molding 9 minutes under 170 DEG C of 1.2MPa.Measure vulcanized article tensile strength
6.5MPa, elongation at break 440%.
Embodiment 7
Ethylene propylene diene rubber（Mitsui, 4045M）100 parts, 5 parts of zinc oxide, 1 part of stearic acid, maleic anhydride grafting three
First 10 parts of EP rubbers, 80 parts prepared of modified abandoned circuit board non-metal powder of embodiment 1, input banbury is kneaded,
Melting temperature is 100 DEG C, and mixing time 8 minutes is cooled to 60 DEG C, adds 1.2 parts of sulphur, 0.5 part of accelerant B Z, accelerator
1.0 parts of DM, 1.2 parts of accelerator CBS, obtained sizing material after mixing is uniform, by sizing material after calendering, extrusion molding 170 DEG C,
Compression molding 9 minutes under 1.2MPa.Measure vulcanized article tensile strength 13.5MPa, elongation at break 410%.
Embodiment 8
Ethylene propylene diene rubber（LG-DOW, 4760）100 parts, 3 parts of zinc oxide, 1.2 parts of stearic acid, methacrylic acid grafting
15 parts of ethylene propylene diene rubber, 120 parts prepared of modification printed circuit board (PCB) non-metal powder of embodiment 2, input banbury is mixed
Refining, melting temperature is 80 DEG C, and mixing time 10 minutes is cooled to 60 DEG C, adds 80 parts of paraffin oil, 0.5 part of sulphur, carbon black 25
Part, sizing material is uniformly made in 0.3 part of Vulcanization accelerator TMTD, 1.2 parts of altax, 1.2 parts of accelerator CBS, mixer mixing afterwards,
By sizing material after calendering, extrusion molding, compression molding 9 minutes under 170 DEG C, 1.2MPa.Measure vulcanized article tensile strength
18.2MPa, elongation at break 350%.
Embodiment 9
Ethylene propylene diene rubber（LG-DOW, 4760）100 parts, 5 parts of zinc oxide, 0.8 part of stearic acid, methacrylic acid grafting
5 parts of ethylene propylene diene rubber, 20 parts of modification printed circuit board (PCB) non-metal powder described in embodiment 3, input banbury is kneaded, and is mixed
It is 160 DEG C to refine temperature, and mixing time 5 minutes is cooled to 60 DEG C, adds 20 parts of naphthenic oil, and 1.5 parts of sulphur, 50 parts of talcum powder promotees
Enter 0.3 part of agent TMTD, sizing material is uniformly made in 1.2 parts of acceterator TE, 1.2 parts of accelerator CBS, mixer mixing afterwards, by sizing material
After calendering, extrusion molding, compression molding 9 minutes under 170 DEG C, 1.2MPa.Measure vulcanized article tensile strength
16.8MPa, elongation at break 430%.
In order to better illustrate the weight that ethylene propylene diene rubber, modified printed circuit board (PCB) non-metal powder are grafted in instant component
Act on, comparative example 1~3 has been investigated respectively on the basis of embodiment 7 not to be added grafting ethylene propylene diene rubber, does not add modification
Printed circuit board (PCB) non-metal powder and the performance impact for adding composite obtained by unmodified printed circuit board (PCB) non-metal powder.
Comparative example 1
Ethylene propylene diene rubber（Mitsui, 4045M）100 parts, 5 parts of zinc oxide, 1 part of stearic acid, embodiment 1 it is prepared it
Modified abandoned 80 parts of circuit board non-metal powder, 1.2 parts of sulphur, 0.5 part of accelerant B Z, 1.0 parts of altax, accelerator
1.2 parts of CBS, after mixer mixing is uniform, 170 DEG C, compression molding 9 minutes under 1.2MPa.Measure vulcanized article tensile strength
5.2MPa, elongation at break 350%.
Comparative example 2
Ethylene propylene diene rubber（Mitsui, 4045M）100 parts, 5 parts of zinc oxide, 1 part of stearic acid, maleic anhydride grafting three
First 10 parts of EP rubbers, 1.2 parts of sulphur, 0.5 part of accelerant B Z, 1.0 parts of altax, 1.2 parts of accelerator CBS, banburying
After machine mixing is uniform, 170 DEG C, compression molding 9 minutes under 1.2MPa.Vulcanized article tensile strength 1.4MPa is measured, elongation is pulled apart
Rate 280%.
Comparative example 3
Ethylene propylene diene rubber（Mitsui, 4045M）100 parts, 5 parts of zinc oxide, 1 part of stearic acid, unmodified printed circuit
80 parts of plate non-metal powder, 1.2 parts of sulphur, 0.5 part of accelerant B Z, 1.0 parts of altax, 1.2 parts of accelerator CBS, banbury
After mixing is uniform, 170 DEG C, compression molding 9 minutes under 1.2MPa.Measure vulcanized article tensile strength 2.5MPa, elongation at break
350%。
The test result of comparative example 1~3 can be shown in Table 1, it is seen then that change for not adding grafting ethylene propylene diene rubber, not adding
Property printed circuit board (PCB) non-metal powder and add composite obtained by unmodified printed circuit board (PCB) non-metal powder, it stretches strong
The difference of degree and elongation at break is obvious.
Table 1
| Embodiment 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Ethylene propylene diene rubber | 100 | 100 | 100 | 100 |
| Zinc oxide | 5 | 5 | 5 | 5 |
| Stearic acid | 1 | 1 | 1 | 1 |
| Maleic anhydride is grafted ethylene propylene diene rubber | 10 | 10 | ||
| Modified abandoned circuit board non-metal powder | 80 | 80 | ||
| Unmodified printed circuit board (PCB) non-metal powder | 80 | |||
| Sulphur | 1.2 | 1.2 | 1.2 | 1.2 |
| Accelerant B Z | 0.5 | 0.5 | 0.5 | 0.5 |
| Altax | 1.0 | 1.0 | 1.0 | 1.0 |
| Accelerator CBS | 1.2 | 1.2 | 1.2 | 1.2 |
| Tensile strength, MPa | 13.5 | 5.2 | 1.4 | 2.5 |
| Elongation at break, % | 410 | 350 | 280 | 350 |
The technical scheme provided above the embodiment of the present invention is described in detail, specific case used herein
Principle and embodiment to the embodiment of the present invention are set forth, and the explanation of above example is only applicable to help and understands this
The principle of inventive embodiments；Simultaneously for those of ordinary skill in the art, according to the embodiment of the present invention, in specific embodiment party
It will change in formula and application, in summary, this specification content should not be construed as limiting the invention.
Claims (7)
1. a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material, it is characterised in that：The composite is
It is made up of the raw material of following parts by weight：
100 parts of ethylene propylene diene rubber；
Modified 20~120 parts of printed circuit board (PCB) non-metal powder；
It is grafted 5~15 parts of ethylene propylene diene rubber；
0~80 part of plasticizer；
0~50 part of filler；
2~5 parts of accelerator；
3~5 parts of zinc oxide；
0.8~1.2 part of stearic acid；
0.5~1.5 part of sulphur；
Wherein, described modification printed circuit board (PCB) non-metal powder is made as follows：
1）Mercaptosilane coupling agents are dissolved in alcohol solvent, alcoholysis is stood, mercaptosilane coupling agents ethanol solution is made；
2）Printed circuit board (PCB) non-metal powder after ball milling, sieving is placed in ozone and activated；
3）By step 2）Printed circuit board (PCB) non-metal powder after activation is placed in homogenizer and stirred, and step is added while stirring
1）Obtained mercaptosilane coupling agents ethanol solution, spontaneously dries, is subsequently placed in oven for drying.
2. a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material according to claim 1, it is special
Levy and be：Step 1）In, the mass percentage concentration of mercaptosilane coupling agents ethanol solution is 1~5%, and the alcoholysis time is 5~30 points
Clock；Step 2）In, soak time is 3~15 minutes；Step 3）In, homogenizer rotating speed is 500~1000 revs/min, is stirred
It is 10~30 minutes, 80~120 DEG C of oven temperature, drying time 1~3 hour, the use of the mercaptosilane coupling agents to mix the time
Measure to be modified the 0.5~1.5% of printed circuit board (PCB) non-metal powder quality, the mercaptosilane coupling agents are mercapto propyl trimethoxy
Silane or mercaptopropyltriethoxysilane.
3. a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material according to claim 1, it is special
Levy and be：Described grafting ethylene propylene diene rubber is selected from maleic anhydride, acrylic or methacrylic acid grafting ethylene propylene diene rubber
In one kind, described grafting ethylene propylene diene rubber gel content is less than 2%, and grafting rate is 2~8%, the grafting ethylene-propylene-diene monomer
Glue is reacted by ethylene propylene diene rubber and grafted monomers under high temperature and high shear force by mercaptan-alkene to be made, described grafting list
Body has following general structure：
Wherein, R is selected from,OrIn one kind.
4. a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material according to claim 3, it is special
Levy and be：Described grafted monomers are made by following steps：
1）By the dissolving of mercaptopropionic acid pentaerythritol ester in organic solvent, it is made into the first solution；
2）Unsaturated carboxylic acid or acid anhydrides are dissolved in organic solvent, and add radical initiator, the second solution is made into；
3）The first solution is heated, the second solution is added dropwise while stirring, continues to react after completion of dropwise addition, organic solvent is removed under reduced pressure,
Produce polyfunctional group grafted monomers；
Wherein, step 1）Described in the first solution mass percentage concentration be 20~60%, step 2）Described in the second solution matter
It is 20~60% to measure percentage concentration, and the addition of the radical initiator is mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid
Or the 0.2~2% of acid anhydrides quality sum, the mol ratio of mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid or acid anhydrides is 1：3, step
Rapid 3）Described in the first solution heating-up temperature be 60~90 DEG C, the reaction time be 0.5~2 hour；
The one kind of described organic solvent in toluene, acetone, ethyl acetate, described unsaturated carboxylic acid or acid anhydrides are selected from horse
The one kind come in acid anhydrides, methacrylic acid or acrylic acid, described radical initiator is that benzoyl peroxide or azo two are different
Butyronitrile.
5. a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material according to claim 3, it is special
Levy and be：Described grafted monomers are made by following steps：
1）By the dissolving of mercaptopropionic acid pentaerythritol ester in organic solvent, it is made into the first solution；
2）By unsaturated carboxylic acid or acid anhydrides dissolving in organic solvent, light trigger is added, the second solution is made into；
3）At normal temperatures, the second solution is slowly added dropwise to the first solution while stirring, while side carries out ultraviolet lighting, knot is added dropwise
Shu Hou, proceeds ultraviolet lighting, and removal of solvent under reduced pressure obtains polyfunctional group grafted monomers；
Wherein, step 1）Described in the first solution mass percentage concentration be 20~60%, step 2）Described in the second solution matter
It is 20~60% to measure percentage concentration, and the light trigger addition is mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid or acid anhydrides
The mol ratio of the 0.2~2% of quality sum, wherein mercaptopropionic acid pentaerythritol ester and unsaturated carboxylic acid or acid anhydrides is 1：3, step
3）Middle time for adding is 30~60 minutes, and it is 10~30 minutes to continue the ultraviolet lighting time；
The one kind of described organic solvent in toluene, acetone, ethyl acetate, described unsaturated carboxylic acid or acid anhydrides are selected from horse
The one kind come in acid anhydrides, methacrylic acid or acrylic acid, described light trigger is selected from light trigger 184,1173,907,659
In one kind.
6. a kind of discarded printed circuit boards non-metal powder/ternary ethlene propyene rubbercompound material according to claim 1, it is special
Levy and be：One or more of the filler in carbon black, white carbon, clay, calcium carbonate, talcum powder, the accelerator choosing
From in accelerator PZ, accelerant B Z, captax, altax, Vulcanization accelerator TMTD, acceterator TE, accelerant CZ, accelerator CBS
One or more；Any one or a few in chlorinated paraffin, paraffin oil, naphthenic oil, aromatic naphtha of described plasticizer.
7. one kind prepares discarded printed circuit boards non-metal powder/ethylene propylene diene rubber as described in any one of claim 1~6 and is combined
The method of material, it is characterised in that including following preparation process：
1）Dispensing：Ethylene propylene diene rubber, modified printed circuit board (PCB) non-metal powder, grafting ethylene-propylene-diene monomer are weighed by mass fraction
Glue, plasticizer, filler, accelerator, zinc oxide, stearic acid, sulphur；
2）Mixing：By ethylene propylene diene rubber, modified printed circuit board (PCB) non-metal powder, grafting ethylene propylene diene rubber, plasticizer, fill out
Material, zinc oxide, stearic acid input banbury are kneaded, and melting temperature is 80~160 DEG C, and mixing time is 5~10 minutes；It is cold
But to sulphur and accelerator after less than 60 DEG C, is added, sizing material is made no more than 80 DEG C in banburying chamber's temperature control；
Vulcanization：By step 2）Prepared sizing material, is vulcanized after calendering, extrusion molding, discarded printed circuit boards is made
Non-metal powder/ternary ethlene propyene rubbercompound material.
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