CN106674946B - A kind of waste printed circuit board nonmetal powder nonloaded silica hydridization filler and the preparation method and application thereof - Google Patents
A kind of waste printed circuit board nonmetal powder nonloaded silica hydridization filler and the preparation method and application thereof Download PDFInfo
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- CN106674946B CN106674946B CN201611269256.8A CN201611269256A CN106674946B CN 106674946 B CN106674946 B CN 106674946B CN 201611269256 A CN201611269256 A CN 201611269256A CN 106674946 B CN106674946 B CN 106674946B
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- circuit board
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of waste printed circuit board nonmetal powder nonloaded silica hydridization fillers and the preparation method and application thereof.Waste and old printed circuit board non-metal powder is distributed in solvent by this method first, then addition ammonium hydroxide and catalyst, after ultrasonic disperse, it is slowly added silicon source monomer, is stirred to react at 30-80 DEG C, centrifugal filtration, washing, drying, obtains waste printed circuit board nonmetal powder nonloaded silica hydridization filler.Prepared hydridization filler is added to the composite material that excellent in mechanical performance is prepared into unsaturated polyester resin.Hydridization filler prepared by the present invention can effectively realize the interface cohesion between waste printed circuit board nonmetal powder and polymeric matrix, significantly improve the mechanical property and thermal stability of composite material.The present invention has far-reaching significance the recycling of waste and old filler and the preparation of novel hybride filler.
Description
Technical field
The invention belongs to the preparations of novel hybride filler and solid waste recycling field, and in particular to a kind of waste printed circuit board
Non-metal powder nonloaded silica hydridization filler and the preparation method and application thereof.
Background technique
With the continuous quickening of electronic product renewal speed, the processing of waste and old printed circuit board (WPCB) also faces huge
Challenge.Currently, precious metal partial is concentrated mainly on for the recycling of WPCB, and the non-metal powder master of content 70% or so
It to be caused serious environmental pollution and the wasting of resources using burning and the treating method of soil-burial.By waste and old printed circuit
Plate non-metal powder (WPCBP) is added in polymeric matrix as reinforced filling prepares composite material, can not only effectively recycle
Using WPCBP, the wasting of resources is reduced, additionally it is possible to which the production cost for reducing polymer composites brings significant economic benefit.
However, the comprehensive performance of polymer composites can be dropped since the interface cohesion between WPCBP and polymeric matrix is poor
It is low, or even deteriorate.Therefore, the surface of WPCBP is pre-processed, enhances its interface cohesion between polymeric matrix with regard to outstanding
It is important.
In addition, polymer composite development be unable to do without inorganic filler extensive use, and with single inorganic filler
It compares, novel hydridization filler usually has more excellent synergy to polymer matrix composite.It is filled out to play hydridization
Material realizes interface cohesion strong between WPCBP and polymeric matrix to composite material humidification outstanding, and the present invention discloses
A method of hydridization filler is prepared in waste printed circuit board nonmetal powder area load silica.It prepares according to the method
Hydridization filler (WPCBP-SiO2) strong interface cohesion effect can be formed with polymeric matrix, significantly improve composite material
Mechanical property and thermal stability.The preparation method of this hydridization filler and in the polymer application be showed no the country so far
Outer document report.
Summary of the invention
It is an object of the invention to overcome the interface cohesion of waste printed circuit board nonmetal powder and matrices of composite material poor, dislike
The shortcomings that changing composite property provides a kind of waste printed circuit board nonmetal powder nonloaded silica hydridization filler and its preparation
Method and application, to by load one layer of irregular nano-silicon dioxide particle come improve composite material mechanical property and
Thermal stability realizes the large-scale application of waste and old printed circuit board non-metal powder in the composite.
WPCBP-SiO of the invention2Hydridization filler is the table using sol-gal process in waste printed circuit board nonmetal powder
Face loads one layer of nano silica protrusion, a kind of hydridization filler of obtained surface imperfection in situ.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of waste printed circuit board nonmetal powder nonloaded silica hydridization filler, comprising the following steps:
Step 1: being distributed in solvent after waste printed circuit board nonmetal powder is crushed drying, adding ammonium hydroxide and catalysis
Agent after ultrasonic disperse, is added dropwise silicon source monomer, is stirred to react under the conditions of 30-80 DEG C；
Step 2: first step products therefrom centrifugal filtration is removed supernatant liquor, wash, drying obtains waste printed circuit
Plate non-metal powder nonloaded silica (WPCBP-SiO2) hydridization filler.
Further, the solvent be water, methanol, ethyl alcohol, acetone, petroleum ether, ethyl acetate, dimethylbenzene, toluene and
The mixed solvent of one or both of pentamethylene；The catalyst is Bis(lauroyloxy)dioctyltin, di lauric dibutyl
One or more of tin and tetrabutylammonium bromide.
Further, the silicon source monomer is one of methyl orthosilicate, ethyl orthosilicate and sodium metasilicate.
Further, it is 3%-10% that the waste printed circuit board nonmetal powder, which is distributed to the solid content in solvent,；The ammonia
The additional amount of water accounts for the 3%-15% of solvent volume；The additional amount of the catalyst is 0.1-1.5ml；The silicon source monomer accounts for useless print
The 50wt%-80 wt% of printed circuit board non-metal powder.
Further, the time of the reaction is 1-10 hours.
Further, the number of the washing is 3-8 times；The drying is to dry 8- in 60-100 DEG C of vacuum drying oven
24h。
A kind of waste printed circuit board nonmetal powder nonloaded silica hydridization as made from above-described preparation method is filled out
Material.
A kind of above-described waste printed circuit board nonmetal powder nonloaded silica hydridization filler answering in the polymer
With, comprising the following steps: waste printed circuit board nonmetal powder nonloaded silica hydridization filler is added to unsaturated polyester (UP) tree
It in rouge, is mixed with three-roll grinder, sequentially adds promotor and curing agent, then after vacuum suction bubble, pour into polytetrafluoroethyl-ne
In alkene mold, room temperature curing 2-4h, in 60-80oSolidify 5-10h in the air dry oven of C, it is nonmetallic to obtain waste printed circuit board
Powder/unsaturated polyester composite.
Further, the unsaturated poly-vinegar resin is that adjacent benzene-type, metaphenylene, p-phenyl and vinyl vinegar type are unsaturated
One or more of poly-vinegar resin.
Further, the curing agent is one in methyl ethyl ketone peroxide, benzoyl peroxide first phthalein and cyclohexanone peroxide
Kind is several；The promotor is one or more of aphthenic acids bores and isooctyl acid bores.
Waste printed circuit board nonmetal powder nonloaded silica hydridization filler prepared by the present invention can effectively realize useless
Interface cohesion between printed circuit board non-metal powder and polymeric matrix, mechanical property and the heat for significantly improving composite material are steady
Qualitative energy.In addition, it is this for the surface treatment method of waste and old filler can further genralrlization to other fillers the modified neck in surface
Domain, the preparation of recycling and novel hybride filler for waste and old filler, all has far-reaching significance.
Compared with prior art, hydridization filler prepared by the present invention has the advantage that and characteristic:
(1) waste printed circuit board nonmetal powder prepared by the present invention/SiO 2 hybrid filler has irregular surface,
Higher specific surface area can form strong interface cohesion effect with polymeric matrix, the growth and extension of crackle be hindered, to multiple
Condensation material mechanical property and thermal stability have active influence.
(2) preparation method of waste printed circuit board nonmetal powder surface in situ load nano silica protrusion simply may be used
Row does not need complicated preparation process and post-processing step, and the silicon dioxide granule on surface is kept away by Si-O chemical bonds
Exempt from occur falling off for silicon dioxide granule in subsequent polymer processing, has expanded the application range of the hydridization filler.
(3) surface treatment of waste printed circuit board nonmetal powder can realize returning for waste and old printed circuit board to a greater extent
It receives and utilizes, have great importance to the reduction wasting of resources and environmental pollution aspect.And the hydridization filler after surface treatment
The performance for significantly improving composite material equally has far-reaching influence in high-performance composite materials application field.
Detailed description of the invention
Fig. 1 a, Fig. 1 b, Fig. 1 c are that waste printed circuit board nonmetal powder nonloaded silica hydridization filler is different in embodiment 1
The SEM of amplification factor schemes.
Fig. 2 is WPCBP and WPCBP-SiO in embodiment 22The hot weight curve of hydridization filler.
Fig. 3 is WPCBP and WPCBP-SiO in embodiment 22The infrared spectrum of hydridization filler.
Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d are WPCBP and WPCBP-SiO in embodiment 32It is added in unsaturated polyester (UP) and impacts
The SEM of section schemes.
Fig. 5 is the stress-strain curve diagram of unsaturated polyester composite in embodiment 4.
Fig. 6 is the thermostabilization curve graph of unsaturated polyester composite in embodiment 4.
Specific embodiment
In order to preferably describe and understand the present invention, below with reference to embodiment and attached drawing, the invention will be further described,
But the scope of protection of present invention is not limited to the scope of the embodiments.
Embodiment 1
5g is crushed dry waste printed circuit board nonmetal powder to be distributed in 100ml dehydrated alcohol, and adds 3.0g
Then 0.2ml dibutyl tin dilaurate, the ultrasonic disperse at 30 DEG C is added dropwise in the ammonium hydroxide of 25wt% and the deionized water of 8.0g
The ethyl orthosilicate of 2.5g is added dropwise at 55 DEG C in 10min, is stirred to react 2.5 hours, product is centrifugated and uses ethanol washing
It five times, is put into 100 DEG C of vacuum drying ovens and dries 10 hours, obtain WPCBP-SiO2Hydridization filler, i.e. waste printed circuit board are nonmetallic
Powder nonloaded silica hydridization filler.Fig. 1 a, Fig. 1 b, Fig. 1 c are that waste printed circuit board nonmetal powder nonloaded silica hydridization is filled out
The SEM of material schemes.It can be seen from the figure that grown one layer of irregular nanometer two on the surface of waste printed circuit board nonmetal powder
Silicon oxide particle, Fig. 1 c can with it is further seen that, silicon dioxide granule is uniformly distributed on non-metal powder surface, rather than simple
Mechanical mixture.
Embodiment 2
In 250 ml three-necked flasks, 10g waste printed circuit board nonmetal powder is added, 150ml dehydrated alcohol is then added,
Then 0.5ml tin dilaurate is added dropwise in 5ml deionized water, the ammonium hydroxide of 10 ml, 25 wt%, ultrasonic disperse 0.5 hour at 30 DEG C
Dibutyl tin, and 8g methyl orthosilicate is added dropwise, it is reacted 10 hours at 30 DEG C, after centrifuge separation, and washs 8 with dehydrated alcohol
It is secondary, it is dried 24 hours in 60 DEG C of vacuum drying ovens, obtains WPCBP-SiO2Hydridization filler.Fig. 2 is WPCBP-SiO2The heat of hydridization filler
Weight curve graph, it can be seen from the figure that the thermal stability of waste printed circuit board nonmetal powder obtains after nonloaded silica particle
It is remarkably reinforced.Fig. 3 is WPCBP and WPCBP-SiO2The infrared spectrum of hydridization filler, it can be seen from the figure that Si-O stretching vibration
Apparent offset all has occurred (from 1032cm in peak-1To 1092cm-1), the change of chemical shift illustrates that silicon dioxide granule passes through
Chemical bond successfully loads to the surface WPCBP, generates new WPCBP-SiO2Hydridization filler.
Embodiment 3
The WPCBP-SiO that will be prepared in 20 g embodiments 12It is poly- that hydridization filler is added to 100g 191# neighbour's benzene-type unsaturation
Ester resin after being mixed with three-roll grinder, sequentially adds 1.0g cobalt iso-octoate promotor, 2.0g methyl ethyl ketone peroxide at normal temperature
Curing agent stirs 5min respectively, after vacuum defoamation processing, pours into progress normal temperature cure 4h in Teflon mould, then puts
Solidify 10h after entering in 60 DEG C of convection ovens, obtains the modified waste printed circuit board nonmetal powder/insatiable hunger of ending isocyanate prepolymer
And polyester composite.Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d are added to the SEM figure of impact fracture surface in unsaturated polyester (UP) matrix, from
As can be seen that the WPCBP of unsupported silica is substantially exposed in unsaturated polyester (UP), with polymeric matrix in Fig. 4 a, Fig. 4 b
Between interface cohesion it is poor, and after area load, the interface cohesion in WPCBP between glass and matrix is remarkably reinforced,
And do not fallen off from the silicon dioxide granule that enlarged drawing can be seen that surface with the processing and forming of polymer, it is this
Irregular surface provides a great help to the promotion of composite property.Table 1 is the mechanical property about composite material.
Table 1
From table 1 it follows that after waste printed circuit board nonmetal powder area load silicon dioxide granule, it is obtained miscellaneous
The mechanical property of composite material can be significantly improved by changing filler.
Embodiment 4
In 500ml three-necked flask, 20g waste printed circuit board nonmetal powder is distributed to 237.5ml dehydrated alcohol, then
The ammonium hydroxide of 15ml25wt%, 12.5ml deionized water, 0.1ml tin dilaurate dioctyl tin, the ultrasonic disperse at 30 DEG C is added
20min obtains suspension, and 13.0g ethyl orthosilicate is added drop-wise in suspension, 1 hour is stirred to react at 80 DEG C, centrifuge washing
It 5 times, is then dried 8 hours in 100 DEG C of vacuum drying ovens, obtains WPCBP-SiO2Hydridization filler.By the WPCBP-SiO of preparation2Addition
To 100g 191# m-phthalate unsaturated polyester resin, after being mixed with three-roll grinder, 1.0g isooctyl acid is sequentially added at normal temperature
Cobalt accelerator, 2.0g methyl ethyl ketone peroxide curing agent stir 5min respectively and pour into polytetrafluoroethylene (PTFE) mould after vacuum defoamation processing
Normal temperature cure 4h is carried out in tool, solidifies 10h after being then placed in 60 DEG C of convection ovens, obtains what ending isocyanate prepolymer was modified
Waste printed circuit board nonmetal powder/unsaturated polyester composite.Fig. 5 is the stress-strain curve diagram about composite material, from
As can be seen that addition WPCBP-SiO in figure2The composite material of hydridization filler, comprehensive performance are obviously improved.Fig. 6 be about
The thermogravimetric curve figure of composite material, it can be seen from the figure that the unsaturated polyester (UP) of preparation is compound after nonloaded silica particle
The thermal stability of material is obviously improved.
Claims (9)
1. a kind of preparation method of waste printed circuit board nonmetal powder nonloaded silica hydridization filler, which is characterized in that including
Following steps:
Step 1: be distributed in solvent after waste printed circuit board nonmetal powder is crushed drying, add ammonium hydroxide and catalyst,
After ultrasonic disperse, silicon source monomer is added dropwise, is stirred to react under the conditions of 30-80 DEG C；
Step 2: first step products therefrom centrifugal filtration is washed, drying, waste printed circuit board nonmetal powder load two is obtained
Aoxidize silicon hybridization filler；
The silicon source monomer is one of methyl orthosilicate and ethyl orthosilicate.
2. a kind of preparation side of waste printed circuit board nonmetal powder nonloaded silica hydridization filler according to claim 1
Method, which is characterized in that the solvent is water, methanol, ethyl alcohol, acetone, petroleum ether, ethyl acetate, dimethylbenzene, toluene and ring penta
The mixed solvent of one or both of alkane；The catalyst be Bis(lauroyloxy)dioctyltin, dibutyl tin dilaurate and
One or more of tetrabutylammonium bromide.
3. a kind of preparation side of waste printed circuit board nonmetal powder nonloaded silica hydridization filler according to claim 1
Method, which is characterized in that it is 3%-10% that the waste printed circuit board nonmetal powder, which is distributed to the solid content in solvent,；The ammonium hydroxide
Additional amount accounts for the 3%-15% of solvent volume；The additional amount of the catalyst is 0.1-1.5ml；The silicon source monomer accounts for useless printing electricity
The 50wt%-80 wt% of road plate non-metal powder.
4. a kind of preparation side of waste printed circuit board nonmetal powder nonloaded silica hydridization filler according to claim 1
Method, which is characterized in that the time of the reaction is 1-10 hours.
5. a kind of preparation side of waste printed circuit board nonmetal powder nonloaded silica hydridization filler according to claim 1
Method, which is characterized in that the number of the washing is 3-8 times；The drying is to dry 8-24h in 60-100 DEG C of vacuum drying oven.
6. a kind of waste printed circuit board nonmetal powder load dioxy as made from the described in any item preparation methods of claim 1-5
SiClx hydridization filler.
7. a kind of waste printed circuit board nonmetal powder nonloaded silica hydridization filler as claimed in claim 6 is in the polymer
Using, which comprises the following steps: waste printed circuit board nonmetal powder nonloaded silica hydridization filler is added to
It in unsaturated polyester resin, is mixed with three-roll grinder, sequentially adds promotor and curing agent, then after vacuum suction bubble,
It pours into Teflon mould, room temperature curing 2-4h solidifies 5-10h in 60-80 DEG C of air dry oven, obtains useless printing
Circuit board non-metal powder/unsaturated polyester composite.
8. application according to claim 7, which is characterized in that the unsaturated poly-vinegar resin be adjacent benzene-type, metaphenylene,
One or more of p-phenyl and vinyl vinegar type unsaturation poly-vinegar resin.
9. application according to claim 7, which is characterized in that the curing agent is methyl ethyl ketone peroxide, benzoyl peroxide
One or more of first phthalein and cyclohexanone peroxide；The promotor be one of cobalt naphthenate and cobalt iso-octoate with
On.
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| CN201611269256.8A CN106674946B (en) | 2016-12-31 | 2016-12-31 | A kind of waste printed circuit board nonmetal powder nonloaded silica hydridization filler and the preparation method and application thereof |
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| CN201611269256.8A CN106674946B (en) | 2016-12-31 | 2016-12-31 | A kind of waste printed circuit board nonmetal powder nonloaded silica hydridization filler and the preparation method and application thereof |
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| CN109135260B (en) * | 2018-08-30 | 2021-05-28 | 深圳市南硕明泰科技有限公司 | Antibacterial and corrosion-resistant composite material for circuit board and preparation method thereof |
| CN112980049B (en) * | 2021-03-24 | 2023-04-25 | 重庆澳彩新材料股份有限公司 | Non-metal powder in-situ copper-removing hybridization modification method for printed circuit board and composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250610A (en) * | 2011-04-25 | 2011-11-23 | 华南师范大学 | Preparation method of composite ZnO-mesoporous silica nanomaterial |
| CN105778338A (en) * | 2016-03-25 | 2016-07-20 | 上海天原集团胜德塑料有限公司 | Environment-friendly soft polyvinyl chloride granules |
| CN106009577A (en) * | 2016-05-31 | 2016-10-12 | 华南理工大学 | Waste printed circuit board nonmetal powder modified room temperature cured unsaturated polyester resin composite material and preparation method thereof |
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- 2016-12-31 CN CN201611269256.8A patent/CN106674946B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250610A (en) * | 2011-04-25 | 2011-11-23 | 华南师范大学 | Preparation method of composite ZnO-mesoporous silica nanomaterial |
| CN105778338A (en) * | 2016-03-25 | 2016-07-20 | 上海天原集团胜德塑料有限公司 | Environment-friendly soft polyvinyl chloride granules |
| CN106009577A (en) * | 2016-05-31 | 2016-10-12 | 华南理工大学 | Waste printed circuit board nonmetal powder modified room temperature cured unsaturated polyester resin composite material and preparation method thereof |
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