CN100547025C - The recoverying and utilizing method of polypropylene composite material and discarded printed circuit boards - Google Patents
The recoverying and utilizing method of polypropylene composite material and discarded printed circuit boards Download PDFInfo
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- CN100547025C CN100547025C CNB2007102019106A CN200710201910A CN100547025C CN 100547025 C CN100547025 C CN 100547025C CN B2007102019106 A CNB2007102019106 A CN B2007102019106A CN 200710201910 A CN200710201910 A CN 200710201910A CN 100547025 C CN100547025 C CN 100547025C
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- -1 polypropylene Polymers 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title description 17
- 239000000843 powder Substances 0.000 claims abstract description 45
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 39
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 17
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000004927 fusion Effects 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
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- 239000008117 stearic acid Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004593 Epoxy Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to the application again of non-metallic material in the electron wastes printed circuit board (PCB), promptly be used to prepare polypropylene composite material, belong to the electron wastes reclaiming and utilize technical field.Polypropylene composite material of the present invention contains following components in weight percentage and is prepared from: 100 parts of polypropylene, 5～30 parts of printed circuit board (PCB) non-metal powders, 6～20 parts of polyolefin elastomers.The present invention is applied in the non-metallic material of printed circuit board (PCB) the regeneration rate that can improve electron wastes in the engineering modification of polypropylene and other plastics greatly, protects environment to greatest extent; Simultaneously can reduce the about 10-30% of material cost; Polypropylene composite material of the present invention has the good notch impact strength performance, though tensile strength, flexural strength and modulus in flexure decrease, but from the overall performance of product application is obviously to improve, and has reached the performance requriements of toughened polypropylene composite.
Description
Technical field
The present invention relates to the application again of non-metallic material in the electron wastes printed circuit board (PCB), promptly be used to prepare polypropylene composite material, belong to the electron wastes reclaiming and utilize technical field.
Background technology
Along with the fast development of electronics technology, the upgrading of various electronic products is frequent day by day.The printed circuit board (PCB) of eliminating in the electronic product that gets off mainly is made up of electronic component, printed circuit board base board and the scolder that connects electronic component and printed circuit board base board.Printed circuit board (PCB) wherein mainly is made up of Resins, epoxy and glass fibre, and printing plate is behind metals such as separate electronic components and parts, copper, silver, and remaining non-metallic material are abandoned or as the filler of low value-added products such as floor.Materials such as glass fibre in the printing plate non-metallic material do not obtain effective regeneration.
According to prediction, the annual production of polypropylene material will reach 7,000,000 tons in 2010, present polypropylene inorganic rigid particle toughening composition is generally selected calcium carbonate particles for use, and other similar toughened systems such as polypropylene/mica, polypropylene/talcum powder, polypropylene/wollastonite and polypropylene/calcium pyroborate etc.Be subjected to the influence of primary ore composition, the fluctuation of mineral rigid particles composition is big, influences performance of composites.Owing to treatment process complexity, the reasons such as will destroying environment of opening a mine, the mineral rigid particles exists all that cost is higher, quality is unstable, problems such as environment friendly difference.
The filling-modified experiment of the single-material of non-metallic material on polypropylene material during Shen Zhi has just waited in paper " Recycling and reusing of nonmetal materials from wasteprinted circuit boards " (CHEMICAL ENGINEERING Vol.34No.10Oct.2006) discarded printed circuit boards, experiment shows that PP after filling-modified is except that flexural strength and tensile strength etc. has by a relatively large margin increase (rigidity increase), the notched Izod impact strength of material descends (toughness decline) significantly, and the workability of material also descends significantly.
Chinese patent: circuit card reclaims powder Seat for manhole cover and manufacture method (application number is 200510038342.3) and a kind of method (application number is 200610011117.5) of the non-metal powder making glass fiber reinforced plastics product of discarded circuit board of utilizing thereof and discloses the method for making kiln well lid and glass reinforced plastic with non-metal powder in the printed circuit board (PCB) respectively, but aforesaid method has been ignored the potential value of non-metallic material, can not form the scale and the demonstration effect of the regeneration of waste electronic product.
Chinese patent: in the waste printed circuit board non-metallic material to utilize method (application number is 200510083981.1) to disclose body material be macromolecular material or material of construction, the matrix material that modification non-metal powder filler and auxiliary agent are prepared from, the non-metallic fillers granularity is 10～400 orders, and mass percent is 10～70%.The notched Izod impact strength of the polypropylene composite material that get according to this patented method preparation according to its specification sheets embodiment 1 record almost there is not variation, is that less raising was arranged in 50% o'clock at non-metal powder filler addition only.
Summary of the invention
To be solved by this invention is the low technical problem of notched Izod impact strength of polypropylene composite material, and polypropylene composite material of the present invention obviously improves than the notched Izod impact strength performance of open polypropylene composite material in the Chinese patent " in the waste printed circuit board non-metallic material utilize method " (application number is 200510083981.1).
The present invention is a kind of new polypropylene composite material for the technical scheme that solves the problems of the technologies described above provides.Polypropylene composite material of the present invention is prepared from by following components in weight percentage: 100 parts of polypropylene, fineness are 200～400 5～30 parts of purpose printed circuit board (PCB) non-metal powders, 6～20 parts of polyolefin elastomers; Also contain 0.2～0.8 part of coupling agent, 0.1～0.6 part of auxiliary agent, coupling agent is used for the modification of non-metal powder, and auxiliary agent is used to improve the workability of matrix material.
Polypropylene composite material of the present invention adopts following method preparation and gets:
It is 200～400 purpose powder that A, printed circuit board (PCB) non-metal powder are pulverized, and the powder dehumidifying adds coupling agent, mixes, and mixture is standby;
B, the mixture of getting the steps A gained mix with polypropylene, polyolefin elastomer, fusion, and granulation, promptly.
The present invention is applied in the non-metallic material of printed circuit board (PCB) the regeneration rate that can improve electron wastes in the engineering modification of polypropylene and other plastics greatly, protects environment to greatest extent; Simultaneously can reduce the about 10-30% of material cost; The regeneration range of application of non-metallic material in the printed circuit board (PCB) is widened in the modification engineering of macromolecular material, can have been saved a large amount of Mineral resources; Because the printed circuit board (PCB) non-metallic material mostly are the non-degradable material, by physics mode regeneration application of printed circuit plate, solved the problem of waste disposal, prevent pollution and destruction to environment.Polypropylene composite material of the present invention has the good notch impact strength performance, though tensile strength, flexural strength and modulus in flexure decrease, but from the overall performance of product application is obviously to improve, and has reached the performance requriements of toughened polypropylene composite.
Embodiment
Polypropylene composite material of the present invention is prepared from by the component of stating weight proportion:
100 parts of polypropylene (PP), 5～30 parts of printed circuit board (PCB) non-metal powders, 6～20 parts of polyolefin elastomers.
According to the component screening experiment, when printed circuit board (PCB) non-metal powder loading level surpasses 30 parts, in the granulation process arch formation can appear, and make granulation be difficult to carry out smoothly, can not reach the normal process state.
Can also add weight proportion in the preparation process of matrix material of the present invention and be 0.2～0.8 part coupling agent.Coupling agent is used for the modification of printed circuit board (PCB) non-metal powder, and coupling agent adopts in silane type coupling agent, aluminate coupling agent or the titanate coupling agent at least a.The printed circuit board (PCB) non-metal powder is after coupling agent treatment, its hydrophilic surface can be changed organic surface of getting married, can avoid particle assembly and the rapid multiviscosisty of polymkeric substance in the system, also can improve the wettability of organic polymer polypropylene the printed circuit board (PCB) non-metal powder.Therefore, common practise according to those skilled in the art, have and to transform printed circuit board (PCB) non-metal powder surface hydrophilicity, prevent that particle in the system from assembling and prevent that the reagent of effects such as the rapid multiviscosisty of polymkeric substance in the system all can be used for the modification of printed circuit board (PCB) non-metal powder.Interpolation is gone up in proper order and should be added coupling agent earlier, then adds auxiliary agent, and auxiliary agent can be but be not limited to be stearic acid, low molecule lipid or white oil, and various components are mixed the performance synergy to obtain preferable result.
The polypropylene that polypropylene composite material of the present invention adopts is homopolymerization or Co-polypropylene, is the base resin as the modification object, adopts two kinds of polypropylene can realize that all matrix material of the present invention is to improving the purpose of notched Izod impact strength performance.
Polyolefin elastomer (be called for short POE) is is catalyzer with the metallocene, by the thermoplastic elastomer that ethene and octene monomer polymerization form, can increase the toughness of matrix material, promptly improve shock strength, but the modulus in flexure of matrix material and intensity can descend all.
One of raw material printed circuit board (PCB) non-metal powder is after printed circuit board (PCB) separating copper and other metals, based on nonmetal mixtures such as glass fibre and solidified epoxy compoundss, through pulverizing is 200～400 purpose particles, forms by the coupling agent activation modification again.The printed circuit board (PCB) non-metal powder plays the enhancement cardinal principle; Glass fibre wherein helps improving the intensity and the dimensional stability of matrix material of the present invention, granular epoxy compounds powder then helps improving the toughness and the surface hardness of matrix material of the present invention, improve modulus in flexure and flexural strength, but the toughness of material can descend.
Glass fibre in POE and the printed circuit board (PCB) non-metal powder, the combination of epoxy compounds can make matrix material of the present invention possess the excellent comprehensive performance; Polypropylene, printed circuit board (PCB) non-metal powder, POE three replenish mutually, and collaborative onset reaches the purpose toughness reinforcing to polypropylene base.
Experimental results show that the matrix material that employing is prepared from by the following weight proportioning: 100 parts of polypropylene, 5～30 parts of printed circuit board (PCB) non-metal powders, 6～20 parts of polyolefin elastomers, 0.2～0.8 part of coupling agent, 0.1～0.6 part of auxiliary agent, can give full play to the effect of synergy between the component, the matrix material overall performance is significantly increased, the notched Izod impact strength of material is significantly improved, especially work as set of dispense than being 100 parts of polypropylene, 25 parts of printed circuit board (PCB) non-metal powders, 16 parts of polyolefin elastomers, 0.5 part of coupling agent, during 0.4 part of auxiliary agent, the overall performance of matrix material of the present invention is higher, and particularly notched Izod impact strength has reached 20.73KJ/m
2
The preparation method of polypropylene composite material of the present invention comprises the steps:
It is 200～400 purpose powder that A, printed circuit board (PCB) non-metal powder are pulverized, and the powder dehumidifying adds coupling agent, mixes, and mixture is standby;
B, the mixture of getting the steps A gained, polypropylene, polyolefin elastomer mix, fusion, and extruding pelletization, promptly; The temperature of wherein fusion, extruding pelletization is 175～225 ℃.
Also can add auxiliary agent in step B mixes with mixture, polypropylene, the polyolefin elastomer of steps A gained.
Promoter addition is 0.1～0.6 part, and auxiliary agent adopts at least a in stearic acid, low molecule lipid or the white oil, is used to improve the workability of matrix material.But also can as other performance that has according to the polypropylene composite material needs, add the conventional corresponding additive of selecting of those skilled in the art according to practical situation.
Adopt above-mentioned raw materials and preparation method to prepare matrix material of the present invention, make glass fibre and Resins, epoxy in the printed circuit board non-metal powder obtain the most effective application, realized the regeneration of waste resource.
Below by component screening description of test polypropylene composite material preparation of the present invention foundation and beneficial effect.
Embodiment 1
Proportioning raw materials: PP 5kg, POE (POE8150 of Dupont-Dow Chemical) 0.3kg, printed circuit board (PCB) non-metal powder (300 order) 0.5kg, commercially available KH792 silane coupling agent 0.01kg, commercially available white oil 0.015kg.
The preparation method of matrix material:
A, will reclaim the printed wiring non-metallic material that copper etc. has the valency heavy metal, be non-metal powder through crushing and classification;
B, non-metal powder dehumidified 0.5 hour in high-speed mixer after, add coupling agent, high-speed mixing 3-5 minute standby;
C, non-metal powder and auxiliary agent after polypropylene, POE, step B handled mix melting mixing in twin screw extruder, extruding pelletization.
Forcing machine (SLF-35B type twin screw extruder, strong macromolecule engineering company of Chengdu section) each section temperature is as follows:
| First section | Second section | Second section | The 4th section | The 5th section | The 6th section | The 7th section |
| 190±5℃ | 210±5℃ | 220±5℃ | 225±5℃ | 220±5℃ | 210±5℃ | 185±5℃ |
Embodiment 2
Proportioning raw materials: PP 5kg, POE 0.6kg, printed circuit board (PCB) non-metal powder (300 order) 1kg, commercially available KH792 silane coupling agent 0.01kg, commercially available white oil 0.01kg.The preparation method is with embodiment 1.
Embodiment 3
Proportioning raw materials: PP 5kg, POE 0.8kg, printed circuit board (PCB) non-metal powder (400 order) 1.25kg, commercially available KH792 silane coupling agent 0.025kg, commercially available white oil 0.02kg.The preparation method is with embodiment 1.
Embodiment 4
Proportioning raw materials sees Table 1, and the preparation method is with embodiment 1.
Table 1 embodiment 4 proportioning raw materials (unit is kg)
Each embodiment preparation and the polypropylene composite material mechanical property experimental results see Table 2
Table 2 polypropylene composite material mechanical property experimental results of the present invention
Because arch formation appears in embodiment 4F and 4I in granulation process, the discharge port of hopper forms the arch bridge shape influences normal discharging, makes granulation be difficult to carry out smoothly, can not reach the normal process state.So do not carry out the mensuration of correlation parameter.
The composite materials property test result of table 3 Chinese patent 200510083981.1 specification sheets embodiment 1 record
| Loading level | Flexural strength Mpa | Modulus in flexure Mpa | Tensile strength Mpa | Notch shock KJ/m 2 |
| 0％ | 47.95 | 1100 | 33.18 | 2.49 |
| 10％ | 46.13 | 1290 | 36.65 | 1.32 |
| 20％ | 49.43 | 1290 | 36.42 | 1.51 |
| 30％ | 69.49 | 1960 | 42.85 | 2.35 |
| 50％ | 81.07 | 2670 | 52.73 | 2.70 |
Data declaration according to table 2, the core material of polypropylene composite material of the present invention is polypropylene, printed circuit board (PCB) non-metal powder and polyolefin elastomer, the three plays the overall performance that main synergy is improved polypropylene composite material, obviously improves notched Izod impact strength.Embodiment 4A～C group and embodiment 4G～I group are compared, whether two groups of differences are to add in the printed circuit board (PCB) non-metal powder coupling agent modified, embodiment 4A～C group obviously improves than embodiment 4G～I group performance, and embodiment 4I is owing to arch formation can occur in granulation process, make granulation be difficult to carry out smoothly, can not reach the normal process state, can't implement.
And the matrix material that table 3 explanation Chinese patent 200510083981.1 specification sheets embodiment 1 are put down in writing at printed circuit board (PCB) non-metal powder addition at 30～50% o'clock, flexural strength, modulus in flexure, tensile strength just increase, but notched Izod impact strength does not obviously improve.
Claims (10)
1. polypropylene composite material is characterized in that, it is to be formed by the feedstock production that comprises following components in weight percentage:
100 parts of polypropylene, 5～30 parts of printed circuit board (PCB) non-metal powders, 6～20 parts of polyolefin elastomers, the fineness of described printed circuit board (PCB) non-metal powder is 200～400 orders.
2. polypropylene composite material according to claim 1 is characterized in that it is prepared from by following components in weight percentage:
100 parts of polypropylene, 25 parts of printed circuit board (PCB) non-metal powders, 16 parts of polyolefin elastomers.
3. polypropylene composite material according to claim 1 and 2 is characterized in that, it also contains weight proportion is 0.2～0.8 part coupling agent.
4. polypropylene composite material according to claim 3 is characterized in that, described coupling agent is at least a in silane type coupling agent, aluminate coupling agent or the titanate coupling agent.
5. polypropylene composite material according to claim 1 and 2 is characterized in that, it also contains weight proportion is 0.1～0.6 part auxiliary agent, and described auxiliary agent is at least a in stearic acid, low molecule lipid or the white oil.
6. polypropylene composite material according to claim 1 and 2 is characterized in that, it also contains weight proportion is 0.1～0.6 part auxiliary agent, 0.2～0.8 part coupling agent;
Wherein, described coupling agent is at least a in silane type coupling agent, aluminate coupling agent or the titanate coupling agent; Described auxiliary agent is at least a in stearic acid, low molecule lipid or the white oil.
7. polypropylene composite material according to claim 6 is characterized in that, it is formed by the feedstock production of forming with following components in weight percentage:
100 parts of polypropylene, 25 parts of printed circuit board (PCB) non-metal powders, 16 parts of polyolefin elastomers, 0.5 part of coupling agent, 0.4 part of auxiliary agent.
8. the preparation method of the described polypropylene composite material of claim 3 is characterized in that it comprises the steps:
It is 200～400 purpose powder that A, printed circuit board (PCB) non-metal powder are pulverized, and the powder dehumidifying adds coupling agent, mixes, and mixture is standby;
B, the mixture of getting the steps A gained mix with polypropylene, polyolefin elastomer, fusion, and extruding pelletization, promptly.
9. the preparation method of polypropylene composite material according to claim 8 is characterized in that, adds auxiliary agent and mix with the mixture of polypropylene, polyolefin elastomer, steps A gained in step B.
10. the preparation method of polypropylene composite material according to claim 9 is characterized in that, the temperature of described fusion of step B and extruding pelletization is 175～225 ℃.
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| CNB2007102019106A CN100547025C (en) | 2007-09-24 | 2007-09-29 | The recoverying and utilizing method of polypropylene composite material and discarded printed circuit boards |
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| CN200710050101 | 2007-09-24 | ||
| CN200710050101.X | 2007-09-24 | ||
| CNB2007102019106A CN100547025C (en) | 2007-09-24 | 2007-09-29 | The recoverying and utilizing method of polypropylene composite material and discarded printed circuit boards |
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| CN101353441B (en) * | 2008-08-26 | 2010-12-15 | 湖南万容科技有限公司 | Method and apparatus for modifying waste printed circuit board composite non-metal powder |
| CN101705006B (en) * | 2009-11-12 | 2011-07-06 | 严志龙 | Glass plastic product with composite material resin circular fiber power |
| CN102161798A (en) * | 2010-02-24 | 2011-08-24 | 郭玉文 | Waste printed circuit board nonmetal powder/polypropylene composite material and preparation method thereof |
| CN102225414A (en) * | 2011-03-31 | 2011-10-26 | 广州市万绿达集团有限公司 | Method for reinforcing waste polyethylene plastics by waste printed circuit board nonmetal powder |
| CN102226025B (en) * | 2011-04-14 | 2014-04-02 | 广州市万绿达集团有限公司 | Method for reinforcing and toughening waste polypropylene plastic by using non-metal powder of waste printed circuit board |
| CN102675736B (en) * | 2012-04-26 | 2014-01-29 | 中国电器科学研究院有限公司 | Recycled composite material for enhancing modified waste polypropylene by using waste printed circuit board powder/glass fiber and preparation method of recycled composite material |
| CN103923378B (en) * | 2013-01-10 | 2016-08-24 | 伟翔环保科技发展(上海)有限公司 | Discarded paper printing circuit board recycling method |
| CN103158311B (en) * | 2013-03-05 | 2015-01-28 | 中国电器科学研究院有限公司 | Waste circuit board powder-based toughening type spraying-free color regeneration composite material and preparation method |
| CN103467918A (en) * | 2013-08-28 | 2013-12-25 | 邬斌 | Non-metal powder modifier for waste circuit board and preparation method of non-metal powder modifier |
| CN105542270B (en) * | 2015-12-04 | 2018-09-11 | 福建师范大学 | A method of waste polyolefine plastics are enhanced using waste printed circuit board nonmetal powder |
| CN108485304A (en) * | 2018-04-26 | 2018-09-04 | 苏州市富荣环保科技有限公司 | A kind of preparation method of the plastic-wood section based on waste and old circuit board toner |
| CN109500050A (en) * | 2018-10-18 | 2019-03-22 | 东莞理工学院 | A kind of waste printed circuit board recycling and reusing preparation composite plate method |
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| CN1792618A (en) * | 2006-01-06 | 2006-06-28 | 清华大学 | Method for mfg. glass fiber reinforced plastic product by nonmetal powder of waste circuit board |
| CN1817957A (en) * | 2005-02-07 | 2006-08-16 | 无锡市鑫乐通讯器材有限公司 | Circuit board recovering powdery material pitcover/base and production thereof |
| CN101007426A (en) * | 2006-12-29 | 2007-08-01 | 南昌晶环材料科技有限公司 | Method for producing building template by chorine and magnesium material |
| CN101037527A (en) * | 2007-03-29 | 2007-09-19 | 上海交通大学 | Method for preparing bakelite by using nonmetal material in waste printing circuit board |
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2007
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817957A (en) * | 2005-02-07 | 2006-08-16 | 无锡市鑫乐通讯器材有限公司 | Circuit board recovering powdery material pitcover/base and production thereof |
| CN1792618A (en) * | 2006-01-06 | 2006-06-28 | 清华大学 | Method for mfg. glass fiber reinforced plastic product by nonmetal powder of waste circuit board |
| CN101007426A (en) * | 2006-12-29 | 2007-08-01 | 南昌晶环材料科技有限公司 | Method for producing building template by chorine and magnesium material |
| CN101037527A (en) * | 2007-03-29 | 2007-09-19 | 上海交通大学 | Method for preparing bakelite by using nonmetal material in waste printing circuit board |
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