CN103450629A - Phenolic moulding powder based on flyash modified phenolic resin and preparation method thereof - Google Patents
Phenolic moulding powder based on flyash modified phenolic resin and preparation method thereof Download PDFInfo
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- CN103450629A CN103450629A CN2012101700577A CN201210170057A CN103450629A CN 103450629 A CN103450629 A CN 103450629A CN 2012101700577 A CN2012101700577 A CN 2012101700577A CN 201210170057 A CN201210170057 A CN 201210170057A CN 103450629 A CN103450629 A CN 103450629A
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- Prior art keywords
- flyash
- resol
- powder
- coupling agent
- phenol formaldehyde
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- 239000010881 fly ash Substances 0.000 title claims abstract description 83
- 239000000843 powder Substances 0.000 title claims abstract description 60
- 238000000465 moulding Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 35
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000002023 wood Substances 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229920003987 resole Polymers 0.000 claims description 47
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 28
- 229920013649 Paracril Polymers 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000005011 phenolic resin Substances 0.000 abstract description 5
- 238000007873 sieving Methods 0.000 abstract description 5
- 229920000459 Nitrile rubber Polymers 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229920001342 Bakelite® Polymers 0.000 description 13
- 239000004637 bakelite Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000206 moulding compound Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of phenolic moulding powder based on flyash modified phenolic resin. For the moulding powder, treated flyash and phenolic resin are in a ratio of 40:60. The treated flyash is chemically composed of, by mass: 50%-60% of SiO2, 25%-30% of Al2O3, 1%-4% of fixed carbon, and the balance a small number of Fe2O3, CaO and MgO. The flyash is subjected to ball-milling to a particle size of less than 200 meshes, and additionally 2.0%-4.0% of a coupling agent KH550 is added to treat the flyash. In addition, nitrile butadiene rubber and wood powder are added. The adding amount of the nitrile butadiene rubber accounts for 6%-14% of the mass of the mixture of the flyash and phenolic resin, and the adding amount of the wood powder accounts for 15%-20% of the mass of the mixture of the flyash and phenolic resin. The materials are mixed and are then subjected to pair roller hot refining on a hot refiner, after cooling and crushing, sieving is conducted, and the power less than 80 meshes can be the phenolic moulding powder product.
Description
Technical field
The present invention relates to flyash utilization of waste material and molding powder technical field, relate in particular to phenol formaldehyde moulding powder based on flyash modified resol and preparation method thereof.
Background technology
Bakelite is widely used in makes various telecommunication apparatus and bakelite goods, as plug, switch, telephone set, instrument case, and general machine button, part etc.Can make various apparatus in dairy industry, for the manufacture of daily living articles such as bottle cap, buttons.Bakelite adds various fillers and makes in resol.Resol hard, crisp, the high temperature residue is low etc., and shortcoming has hindered its application in high performance composite.Therefore, be necessary to select a kind of weighting agent to improve its performance, reduce the cost of bakelite simultaneously.
At present. approximately hundred million tons of China coal-burning power plant discharge in every year flyash industrial residues, except part is used for building material industry, as lay bricks, hang down outside trade mark cement, pavior etc., much be stacked in addition storage ash, perhaps enter among rivers,lakes and seas, both occupied farmland, again contaminate environment.The further comprehensive utilization of development powder coal ash, turn waste into wealth for this reason, is when last extremely urgent task.
At present, Technology of Comprehensive Utilization of Coal Ash is in continuous progress, and approach is continued to optimize.There is enterprise successively to utilize fly ash development to go out novel wall material, concrete and mortar adulterant, also be widely used in manufacture of cement, build the road, backfill etc., wherein, most effective as the utilization of fly ash that in mortar and concrete, the adulterant place of cement is used, maximum to the energy-saving and emission-reduction contribution.Chinese patent CN1315300, CN1306031A has proposed a kind of method of utilizing flyash and the compound PVC of the preparation substituted for plastic of polyethylene, and Chinese patent CN1315243 has proposed to utilize the method for the standby well cover of coal ash for manufacturing.
Adopt calcium carbonate-filled resol can improve the performance of resol, but need the larger cost of cost.And flyash is refuse, cost is very low.Utilize flyash to add a small amount of coupling agent etc. to carry out modification to resol as filler simultaneously; prepare the bakelite substitute products and can reach the purpose that reduces the phenoplast cost; can also improve various machinery and the mechanical property of phenoplast simultaneously; also opened up the Yi Tiaoxin road for the comprehensive utilization of flyash; accomplish utilization of waste material; protect environment, there is environmental economical profit preferably.The product phenol formaldehyde moulding powder made, can be used as the equivalent material of bakelite, greatly saved the cost of buying bakelite, can improve the property indices of bakelite simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of phenol formaldehyde moulding powder based on flyash modified resol and preparation method thereof.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of phenol formaldehyde moulding powder based on flyash modified resol, described molding powder is 40:60 in the ratio of processed flyash and resol; The chemical composition mass percent of described processed flyash is: SiO
250%-60%, Al
2o
325%-30%, fixed carbon content 1%-4%, all the other are a small amount of Fe
2o
3, CaO, MgO, the flyash granularity is less than 200 orders, additional coupling agent, the 2.0%-4.0% that described coupling agent add-on is flyash quality.
Described molding powder is additional paracril again, the 6%-14% that described paracril add-on is flyash and resol mixture quality.
Described molding powder is additional wood powder again, the 15%-20% that described wood powder add-on is flyash and resol mixture quality.
Described coupling agent is coupling agent KH550.
A kind of phenolic molding compound powder, preparation method thereof based on flyash modified resol, described molding powder is 40:60 in the ratio of processed flyash and resol;
The chemical composition mass percent of described processed flyash is: SiO
250%-60%, Al
2o
325%-30%, fixed carbon content 1%-4%, all the other are a small amount of Fe
2o
3, CaO, MgO, flyash is milled to granularity and is less than 200 orders, additional coupling agent, the 2.0%-4.0% that described coupling agent add-on is flyash quality, processed flyash, described coupling agent is coupling agent KH550;
Additional paracril and wood powder again, the 6%-14% that described paracril add-on is flyash and resol mixture quality, the 15%-20% that described wood powder add-on is flyash and resol mixture quality;
Carry out the pair roller heat refining after will above-mentioned substance mixing on warm-up mill, after cooling crush, by screening, 80 orders are following is described phenol formaldehyde moulding powder product.
Flyash in the present invention is through the treating processes of coupling agent, coupling agent can connect organism and inorganics, the larger molecular organics that contains the part coal in flyash, in the process of heat refining, the macromole of coal can react and generate firmly chemical bond with resol, in addition, the processing of coupling agent also makes inert molecule in flyash (as Al
2o
3, SiO
2deng) effective dispersed coming, improve the interface binding power of flyash and resin matrix, thereby be conducive to improve comprehensive mechanical property and the processing characteristics of phenol formaldehyde moulding powder.
In order to strengthen the toughness that makes the phenol formaldehyde moulding powder product, paracril is added into; In order to increase the insulativity of material, also added wood powder.
The present invention takes full advantage of the trade waste flyash that coal-burning power plant produces, and greatly reduces the cost of producing phenol formaldehyde moulding powder, is conducive to the protection of environment, has prepared a kind of phenol formaldehyde moulding powder product that can substitute bakelite simultaneously.
Compared with prior art, its beneficial effect is phenol formaldehyde moulding powder based on flyash modified resol of the present invention:
1, waste flyash coal-burning power plant produced is used for modified phenolic resins and produces the phenol formaldehyde moulding powder product, has fully utilized power plant's industrial waste flyash, has protected environment, has saved cost for the production of phenolaldehyde moulding compound simultaneously.
2, the phenol formaldehyde moulding powder product of preparing can reach the index request of bakelite, can substitute bakelite.
3, the coupling agent that is used as the bridge that hydroaropic substance and lyophobic dust mutually combine is processed flyash, the dispersed favourable condition that provides for flyash in resol, thus be conducive to the intensity of the phenolaldehyde moulding compound that the flyash filled phenolic resin generates and the raising of toughness.
4, in the process of heat refining, the organic meeting of the macromole of part coal and resol generation chemical action in flyash, thus generate more firmly chemical bond, be conducive to the combination between flyash and resol.
5, owing to there being a large amount of organic lignocelluloses in wood powder, in the process of heat refining with flyash in macromole and the resol generation crosslinking reaction of coal, thereby can improve preferably the fragility of resol.
6, as the fragility that can improve preferably resol that adds of the paracril of visco-elastic material, increase its toughness.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Get 40 parts, the flyash of granularity below 200 orders processed containing the aqueous solution of 2.0% coupling agent KH550, SiO in described flyash
2mass percent is 50%, Al
2o
3mass percent is 25%, and fixed carbon content is 1%, and surplus is Fe
2o
3, CaO, MgO; 60 parts, resol, 18% the wood powder that adds flyash and resol mixture quality, 8% the paracril that simultaneously adds flyash and resol mixture quality, add and mediate the warm-up mill heat refining after these materials are mixed, heat refining material cooling crush, by after sieving, obtains the following phenol formaldehyde moulding powder of 80 orders.Obtained phenol formaldehyde moulding powder is carried out to Performance Detection, its main performance index: flexural strength is 77Mpa, and shock strength is 1.59kJ/m
2, water-intake rate is 36mg, relative density 1.44,147 ℃ of heat-drawn wires, insulation resistance 1.2 * 10
8Ω, mobility 92mm.
Embodiment 2
Get 40 parts, the flyash of granularity below 200 orders processed containing the aqueous solution of 2.5% coupling agent KH550, SiO in described flyash
2mass percent is 55%, Al
2o
3mass percent is 25%, and fixed carbon content is 3%, and surplus is Fe
2o
3, CaO, MgO; 60 parts, resol, 16% the wood powder that adds flyash and resol mixture quality, 10% the paracril that simultaneously adds flyash and resol mixture quality, add and mediate the warm-up mill heat refining after these materials are mixed, heat refining material cooling crush, by after sieving, obtains the following phenol formaldehyde moulding powder of 80 orders.Obtained phenol formaldehyde moulding powder is carried out to Performance Detection, and its main performance index flexural strength is 74Mpa, and shock strength is 1.53kJ/m
2, water-intake rate is 27mg, relative density 1.39,151 ℃ of heat-drawn wires, insulation resistance 1.8 * 10
8Ω, mobility 112mm.
Embodiment 3
Get 40 parts, the flyash of granularity below 200 orders processed containing the aqueous solution of 2.0% coupling agent KH550, SiO in described flyash
2mass percent is 60%, Al
2o
3mass percent is 30%, and fixed carbon content is 4%, and surplus is Fe
2o
3, CaO, MgO; 60 parts, resol, 18% the wood powder that adds flyash and resol mixture quality, 14% the paracril that simultaneously adds flyash and resol mixture quality, after being mixed, these materials add pair roller warm-up mill heat refining, heat refining material cooling crush, by after sieving, obtains the following phenol formaldehyde moulding powder of 80 orders.Obtained phenol formaldehyde moulding powder is carried out to Performance Detection, and its main performance index flexural strength is 72Mpa, and shock strength is 1.4kJ/m
2, water-intake rate is 30mg, relative density 1.43,148 ℃ of heat-drawn wires, insulation resistance 3.5 * 10
8Ω, mobility 130mm.
Embodiment 4
Get 40 parts, the flyash of granularity below 200 orders processed containing the aqueous solution of 2.0% coupling agent KH550, SiO in described flyash
2mass percent is 60%, Al
2o
3mass percent is 30%, and fixed carbon content is 4%, and surplus is Fe
2o
3, CaO, MgO; 60 parts, resol, 16% the wood powder that adds flyash and resol mixture quality, 6% the paracril that simultaneously adds flyash and resol mixture quality, after being mixed, these materials add pair roller warm-up mill heat refining, heat refining material cooling crush, by after sieving, obtains the following phenol formaldehyde moulding powder of 80 orders.Obtained phenol formaldehyde moulding powder is carried out to Performance Detection, and its main performance index flexural strength is 70Mpa, and shock strength is 1.47kJ/m
2, water-intake rate is 31mg, relative density 1.35,154 ℃ of heat-drawn wires, insulation resistance 1.4 * 10
8Ω, mobility 125mm.
The phenol formaldehyde moulding powder product performance that make by above proportioning processing are detected, its detection method is mainly according to GB1040-79, GB1048-79, the national standards such as GB1039-79 are detected, and its result is as shown in table 1, its performance index reach the requirement of phenol formaldehyde moulding powder, can substitute the bakelite product of existing market fully, and cheap more than the cost of bakelite, thus can better utilised flyash, eliminate its pollution to environment, for enterprise creates larger economic benefit.
Table 1
| Sequence number | The performance title | Numerical value |
| 1 | Relative density | 1.35-1.45 |
| 2 | Flexural strength MPa | 70-80 |
| 3 | Shock strength (breach) kJ/m 2 | 1.4-1.6 |
| 4 | Heat-drawn wire ℃ | 145-155 |
| 5 | Insulation resistance Ω | 10 8-10 10 |
| 6 | Water-absorbent mg | 25-40 |
| 7 | Mobility (La Xige) mm | 80-140 |
| 8 | The granularity order | Below 80 |
Claims (5)
1. the phenol formaldehyde moulding powder based on flyash modified resol, it is characterized in that: described molding powder is 40:60 in the ratio of processed flyash and resol; The chemical composition mass percent of described processed flyash is: SiO
250%-60%, Al
2o
325%-30%, fixed carbon content 1%-4%, all the other are a small amount of Fe
2o
3, CaO, MgO, the flyash granularity is less than 200 orders, additional coupling agent, the 2.0%-4.0% that described coupling agent add-on is flyash quality.
2. the phenol formaldehyde moulding powder based on flyash modified resol according to claim 1, it is characterized in that: described molding powder is additional paracril again, the 6%-14% that described paracril add-on is flyash and resol mixture quality.
3. the phenol formaldehyde moulding powder based on flyash modified resol according to claim 1 and 2, it is characterized in that: described molding powder is additional wood powder again, the 15%-20% that described wood powder add-on is flyash and resol mixture quality.
4. the phenol formaldehyde moulding powder based on flyash modified resol according to claim 1, it is characterized in that: described coupling agent is coupling agent KH550.
5. the phenolic molding compound powder, preparation method thereof based on flyash modified resol is characterized in that:
Described molding powder is 40:60 in the ratio of processed flyash and resol;
The chemical composition mass percent of described processed flyash is: SiO
250%-60%, Al
2o
325%-30%, fixed carbon content 1%-4%, all the other are a small amount of Fe
2o
3, CaO, MgO, flyash is milled to granularity and is less than 200 orders, additional coupling agent, the 2.0%-4.0% that described coupling agent add-on is flyash quality, processed flyash, described coupling agent is coupling agent KH550;
Additional paracril and wood powder again, the 6%-14% that described paracril add-on is flyash and resol mixture quality, the 15%-20% that described wood powder add-on is flyash and resol mixture quality;
Carry out the pair roller heat refining after will above-mentioned substance mixing on warm-up mill, after cooling crush, by screening, 80 orders are following is described phenol formaldehyde moulding powder product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101700577A CN103450629A (en) | 2012-05-29 | 2012-05-29 | Phenolic moulding powder based on flyash modified phenolic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101700577A CN103450629A (en) | 2012-05-29 | 2012-05-29 | Phenolic moulding powder based on flyash modified phenolic resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103450629A true CN103450629A (en) | 2013-12-18 |
Family
ID=49733492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101700577A Pending CN103450629A (en) | 2012-05-29 | 2012-05-29 | Phenolic moulding powder based on flyash modified phenolic resin and preparation method thereof |
Country Status (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118509A (en) * | 2017-05-27 | 2017-09-01 | 贵州大学 | Tea saponin modification converter slag and its composite floor board being made with waste or used plastics |
| CN107118506A (en) * | 2017-05-27 | 2017-09-01 | 贵州大学 | Tea saponin modification blast furnace slag and its composite floor brick being made with waste or used plastics |
| CN111334090A (en) * | 2020-02-26 | 2020-06-26 | 上海应用技术大学 | Modified fly ash and preparation method thereof |
| EP3822314A1 (en) | 2019-11-18 | 2021-05-19 | Patenta Asia Ltd. | Zusammensetzung, sowie deren verwendung zur herstellung einer mehrschichtplatte |
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2012
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118509A (en) * | 2017-05-27 | 2017-09-01 | 贵州大学 | Tea saponin modification converter slag and its composite floor board being made with waste or used plastics |
| CN107118506A (en) * | 2017-05-27 | 2017-09-01 | 贵州大学 | Tea saponin modification blast furnace slag and its composite floor brick being made with waste or used plastics |
| CN107118509B (en) * | 2017-05-27 | 2018-12-28 | 贵州大学 | Tea saponin modification converter slag and its with composite floor board made of waste plastic |
| CN107118506B (en) * | 2017-05-27 | 2019-01-25 | 贵州大学 | Tea saponin modified blast furnace slag and its composite floor tiles made of waste plastics |
| EP3822314A1 (en) | 2019-11-18 | 2021-05-19 | Patenta Asia Ltd. | Zusammensetzung, sowie deren verwendung zur herstellung einer mehrschichtplatte |
| WO2021099373A1 (en) | 2019-11-18 | 2021-05-27 | Patenta Asia Ltd. | Composition, and use thereof for producing a multilayer board |
| CN111334090A (en) * | 2020-02-26 | 2020-06-26 | 上海应用技术大学 | Modified fly ash and preparation method thereof |
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Application publication date: 20131218 |