CN114075364A - Method for manufacturing recycled and reused phenolic aldehyde type waste and environment-friendly bakelite phenolic aldehyde material - Google Patents
Method for manufacturing recycled and reused phenolic aldehyde type waste and environment-friendly bakelite phenolic aldehyde material Download PDFInfo
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- CN114075364A CN114075364A CN202010832153.8A CN202010832153A CN114075364A CN 114075364 A CN114075364 A CN 114075364A CN 202010832153 A CN202010832153 A CN 202010832153A CN 114075364 A CN114075364 A CN 114075364A
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- 239000002699 waste material Substances 0.000 title claims abstract description 124
- 239000000463 material Substances 0.000 title claims abstract description 75
- 229920001342 Bakelite® Polymers 0.000 title claims abstract description 72
- 239000004637 bakelite Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 46
- -1 phenolic aldehyde Chemical class 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000000835 fiber Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011889 copper foil Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000005034 decoration Methods 0.000 claims abstract description 6
- 230000007613 environmental effect Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 101
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 92
- 239000011343 solid material Substances 0.000 claims description 62
- 238000007731 hot pressing Methods 0.000 claims description 58
- 229920002522 Wood fibre Polymers 0.000 claims description 51
- 239000002025 wood fiber Substances 0.000 claims description 48
- 239000002861 polymer material Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 27
- 238000005553 drilling Methods 0.000 claims description 26
- 229920001568 phenolic resin Polymers 0.000 claims description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 19
- 239000005011 phenolic resin Substances 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002023 wood Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 8
- 239000010432 diamond Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011094 fiberboard Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 239000002154 agricultural waste Substances 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
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- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000003637 basic solution Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 230000001815 facial effect Effects 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 230000001012 protector Effects 0.000 claims 1
- 238000009966 trimming Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 20
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- 238000010276 construction Methods 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 3
- 230000000295 complement effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
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- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000011120 plywood Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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Abstract
A process for reclaiming the phenolic aldehyde waste and the bakelite in environment protection mode includes such steps as crushing and grinding the phenolic aldehyde waste and other fibrous materials to obtain particles, mixing them together, adding resin, mixing, and conventional plastic material. The invention can complement the situation that the traditional structure is mainly composed of waste bakelite waste or waste fiber, which is easy to distribute unevenly or has insufficient strength. The invention can be applied to plates used in the manufacture of printed circuit boards and copper foil substrates or applied to the way commonly used by bakelite, and can be used as a novel environment-friendly bakelite plate. Also can be used as a plate for decoration and construction, or used for external wall heat preservation and the like. The regenerated material has the characteristics that by the process, the regenerated material can be repeatedly reproduced and recycled continuously, so that the environmental load is effectively reduced.
Description
Technical Field
The present invention relates to the recycling of phenolic type waste materials, and more particularly to a method for recycling and reusing phenolic type waste materials and environmentally friendly bakelite phenolic materials. The method can effectively recycle phenolic aldehyde type waste materials and simultaneously recycle other types of fiber waste materials so as to achieve the aim of recycling.
Background
From the perspective of environmental engineering, waste is a resource that is misplaced. It is very difficult to recycle resources in a proper way to make usable and usable products. Especially thermoset plastic articles. There are almost only two final disposal modes, landfill and incineration. Countless manufacturers expect that the manufacturers can recycle and reuse the used phenolic aldehyde boards (commonly called bakelite boards) while selling the phenolic aldehyde boards. The phenolic aldehyde bakelite plate is thermosetting engineering plastic. The characteristic of the incinerator is that the incineration temperature is high, and the characteristic of the high heat value easily causes the damage of the incinerator body, and exceeds the designed heat value of the incinerator. Thus reducing the willingness of the clearing industry to collect the wastes and enter most incinerators for final treatment.
Phenolic aldehyde board (commonly called bakelite board) is a thermosetting plastic formed by polymerizing phenol and aldehyde as raw materials to prepare phenolic resin, impregnating paper or cloth with the phenolic resin, drying and hot-pressing the impregnated paper or cloth to form the phenolic resin. Phenolic materials (phenolic boards or bakelite boards) are widely used in the printed circuit board industry as protective boards for drilling and forming processes and for protecting products by using upper and lower pads. The bakelite board with the backing plate type using mode still accords with the original material characteristics after mechanical drilling, and the material is not changed after the geometric three-dimensional shape is subjected to the processes of drilling, forming and the like of the printed circuit board. Phenolic materials (phenolic boards or bakelite boards) are also widely used in insulation, thermal insulation and other industries.
In general, the used bakelite waste (or phenolic resin type waste) in the forms of drilling, molding, or powder, scrap, etc. has little benefit in achieving recycling in a direct use manner because the geometry that can be used has been destroyed. In order to effectively increase the availability of the tail section, the bakelite powder formed by pulverizing and grinding the bakelite waste to fine powder occupies most of fiber pores in a microscopic scale, so that the subsequent direct addition of the resin is caused, and the binding property is very weak whether the pressing is carried out or not. The method is easy to form huge cracks under slight force application even in the gluing process, and the method for reusing the tail end is directly limited.
Because the above products are easy to form cracks, holes or obvious product defects with insufficient strength and the like when being reshaped, and the situation that the carbon dioxide capture amount is reduced due to felling forest lands based on the requirement of the global wood industry, the invention hopes to provide a method for recycling waste phenolic aldehyde type waste (bakelite waste), which can be used together with other waste fiber boards after drilling by recycling the recycled phenolic aldehyde engineering plastic type waste, especially the waste phenolic aldehyde boards after drilling, such as bakelite boards, bakelite strips, powder generated during drilling of bakelite, and the like. So as to widely increase the recycling property of the waste fiber and achieve the aim of recycling economy and the concept of environmental persistence.
Disclosure of Invention
Therefore, the present invention is directed to solve the above problems of the prior art, and the present invention provides a method for recycling and reusing phenolic waste and environment-friendly bakelite phenolic material, wherein the phenolic waste (i.e., bakelite waste) and other fiber materials (preferably waste fibers) are crushed and ground to a specific particle size, and then mixed uniformly in a specific powder mixing ratio, and then added with a resin, and the waste bakelite waste is used as a main raw material of a new product when the waste bakelite waste is supplemented with the resin in a specific resin mixing ratio, so that the problems of defects caused by uneven distribution and weak structure are easily generated after the new resin is added. And the situation that the strength of the product is insufficient when the waste fiber is taken as the main structure can be avoided. And then the final environment-friendly bakelite phenolic material finished product is prepared by a traditional plastic material manufacturing method.
The present invention can also be used to further destroy and treat the phenolic type waste (or bakelite waste) by properly crushing and grinding the phenolic type waste (or bakelite waste) and other fiber materials to a specific particle size, and then adding acid or alkali in a specific mixing ratio. After the original phenolic aldehyde type waste is corroded, the number of holes is increased and the effect of fiber decomposition is achieved. The fiber material can be added additionally, so that the cracks caused by the problems of poor resin binding property and non-uniformity are improved. And after being uniformly mixed, adding new resin according to a specific resin mixing proportion, and preparing the environment-friendly bakelite phenolic material finished product by a traditional plastic material preparation method.
The specific resin mixing ratio, which is the weight ratio of the total weight of the phenolic type waste (or bakelite waste) powder and the fiber type material (preferably waste fiber) powder to the weight of the newly added resin, may be in the range of 0.01 to 0.99, but is not limited thereto.
The addition of the resin can be phenolic resin, urea-formaldehyde resin, epoxy resin, acrylic resin and other resin types. Also can be a bridging agent. But is not limited to, the aforementioned resins, types of bridging agents, or mixtures thereof. It may be a solid resin or a liquid resin. Wherein the resin is preferably a phenolic resin.
The traditional plastic material is prepared by mixing solid resin with ground mixed sieved powder, or soaking ground mixed sieved powder in liquid resin, separating, drying, molding with a mold without limitation, and performing batch hot pressing or cold pressing molding, or continuous hot pressing or cold pressing molding. In the case of hot or cold pressing, the pressure may be 0.01 kg/cm2To 300 kg/cm2And (3) a range. Or by injecting the material through an injection machine, or by extruding the material through an extruder. Or foamed as a foamed material. May be, but is not limited to, the aforementioned plastic production process.
The environment-friendly bakelite phenolic material finished product comprises but is not limited to a lower drilling liner plate, an upper cover plate, a desktop plate and a cutting liner plate which are applied to the manufacture procedures of printed circuit boards and copper foil substrates, or comprises but is not limited to a mode generally used by bakelite, such as a clamp, a jig, a heat insulation material and an insulating material, and is applied to a novel environment-friendly bakelite plate. But also can include but is not limited to the board used for decoration construction, such as plywood, wood core board, particle board, melamine board, fiber board, foaming board, floor, etc.; or a board for furniture; or for the purposes of external wall heat preservation and the like, and is regarded as a novel phenolic aldehyde bakelite material or a regenerated wood or material. Or a regenerated material formed by common plastic manufacturing processes such as a mould, a jig, injection, extrusion and the like. In addition, the regenerated material has the characteristics of continuous and repeated reproduction and recycling by the process. Thereby effectively reducing the environmental load.
In order to achieve the above object, the present invention provides a method for producing an environment-friendly bakelite phenolic material by recycling and reusing phenolic waste, comprising the steps of: step A: crushing and powdering the waste phenolic aldehyde polymeric material to form powder; and B: crushing and powdering wood fibers to form powder; and C: then mixing the powder of the waste phenolic polymer material with the powder of the wood fiber, wherein the mixing weight ratio of the two is in the range of 0.01 to 0.99; step D: then adding resin, and uniformly mixing the powder of the waste phenolic aldehyde polymeric material, the powder of the wood fiber and the resin, wherein the resin is mainly used for bonding the powder of the waste phenolic aldehyde polymeric material and the powder of the wood fiber; step E: and (3) applying one of hot pressing, cold pressing, injection by an injection machine, extrusion by an extrusion machine or foaming to the obtained mixture to form the required solid material.
The invention also provides an environment-friendly bakelite phenolic structure which is a flat plate structure with a specific geometric shape, wherein the environment-friendly bakelite phenolic structure is a thick flat plate with a fixed geometric shape, and the shape is selected from any one of polygons of rectangles, squares, circles, rhombuses and triangles; the environment-friendly bakelite phenolic structure is a flat plate structure formed by mixing waste phenolic polymeric materials, wood fibers and resin; wherein the weight ratio of the powder of the waste phenolic polymeric material mixed with the powder of the wood fiber is in the range of 0.01 to 0.99; wherein the weight ratio of the resin is more than 0.01.
A further understanding of the nature and advantages of the present invention will become apparent from the following description when read in conjunction with the accompanying drawings.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows a flow chart of the steps of the manufacturing method of the present invention.
FIG. 2 shows a schematic of the flat panel structure of the present invention.
FIG. 3 is a schematic diagram of another embodiment of a plate structure according to the present invention.
FIG. 4 is a schematic diagram of another embodiment of a plate structure according to the present invention.
FIG. 5 is a schematic diagram of another embodiment of a plate structure according to the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings, wherein the same reference numerals are used to designate the same elements, components, and advantages thereof.
Referring to fig. 1, a method for recycling and reusing phenolic type waste and environment-friendly bakelite phenolic material according to the present invention is shown, comprising the following steps:
step 100: the waste phenolic polymer material is crushed and powdered to form powder. Wherein the particle size of the waste phenolic polymer material powder can be 1-200 mesh, preferably the particle size of the waste phenolic polymer material powder is 200 mesh or above. However, the present invention is not limited to the specific range of the particle size of the waste phenolic polymer powder, and the particle size of the waste phenolic polymer powder may be a combination of the specific ratios of the above ranges. For example, the waste phenolic aldehyde polymer material is screened by a 200-mesh screen, and the particle size of the waste phenolic aldehyde polymer material accounts for 60 percent of the total waste phenolic aldehyde polymer material powder; and screening the waste phenolic aldehyde polymeric material through a 100-200 mesh screen, wherein the particle size of the waste phenolic aldehyde polymeric material accounts for 40% of the total waste phenolic aldehyde polymeric material powder.
The waste phenolic aldehyde polymer material is bakelite waste and may be used in making upper phenolic aldehyde cover plate, lower phenolic aldehyde base plate, tabletop plate or cutting protecting base plate for copper foil base plate. The waste phenolic polymeric material is not limited to the above-mentioned sources of phenolic-type waste material. Mainly used for recycling the phenolic aldehyde polymer material after industrial treatment.
Step 110: the wood fiber (namely the waste wood pulp board material after the printed circuit board drilling process) is crushed and powdered to form powder. Wherein the particle size of the powder of the wood fiber can be 1 to 200 mesh, preferably the particle size of the powder of the wood fiber is 200 mesh or more. However, the present invention is not limited to the specific range of the particle size of the wood fiber powder, and the particle size of the wood fiber powder may be a combination of the specific ratios of the above ranges. For example, the wood fiber powder is screened by a 200-mesh screen, and the particle size of the wood fiber powder accounts for 80% of the total waste phenolic polymer material powder; and screening the powder of the wood fiber through a 100-200 mesh screen, wherein the particle size of the powder accounts for 20% of the total amount of the waste phenolic polymer material powder.
The wood fiber can be a lower backing plate, a waste wood pulp plate, an environment-friendly plate or other types of fiber plates used in mechanical drilling process in printed circuit board manufacturing industry. The wood fiber can also be a board used in the decoration industry, the construction industry, the wood industry and the furniture industry, such as a board, a plywood, a core board, a particle board, a melamine board, a fiberboard and the like which are discarded, but not limited to be a discarded source, and can also be a fresh fiber source, such as wood powder and wood dust, or agricultural wastes, such as rice straw and bagasse. But not limited to, all of the aforementioned sources of wood fiber. More suitable wood fiber source is waste wood pulp board, environment-friendly board or fresh wood powder after mechanical drilling process.
Step 120: the powder of the waste phenolic polymeric material is then mixed with the powder of the wood fibre. The weight ratio of the two mixed may be in the range of 0.01 to 0.99 (i.e. the powder of the waste phenolic polymer material/the powder of the wood fiber is in the range of 0.01 to 0.99), but is not limited to this range. For example, the powder of the waste phenolic polymer material and the powder of the wood fiber are uniformly mixed in an equal manner (1 kg of the powder of the waste phenolic polymer material and 1 kg of the powder of the wood fiber) by using a homogenizer.
Step 130: then adding a proper amount of resin, and uniformly mixing the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin by using a homogenizer. Wherein the resin is mainly used for binding the powder of the waste phenolic polymer material and the powder of the wood fiber. When the proportion of the resin is higher, the degree of adhesion is better, but the cost is higher and the recovery rate of waste utilization is lower. For example, 1 kg of waste phenolic polymer material powder is mixed with 1 kg of wood fibre powder and then 1 kg of resin is added.
Wherein the resin may be a solid or liquid resin, preferably a solid resin. The resin can be phenolic resin, urea-formaldehyde resin, epoxy resin, acryl resin, or a mixture thereof. Wherein the resin is preferably a phenolic resin. When the resin is a phenolic resin, the amount of formaldehyde to phenol in the phenolic resin has a molar ratio (F/P ratio) in the range of 0.1: 1 to 3.0: preferably 1. More specifically, the molar ratio of the formaldehyde to the phenol is 0.1: 1 to 1.0: the solid phenolic resin of 1 is preferable. Or the molar ratio of the formaldehyde to the phenol is 1.0: 1 to 3.0: the liquid phenolic resin of 1 is preferred. Or a mixture of the two aforementioned major types of resins or states in any combination ratio.
After the resin is added in step 130, a bridging agent may be further added to form a three-dimensional structure.
Step 140: and (3) applying one of hot pressing, cold pressing, injection by an injection machine, extrusion by an extrusion machine or foaming to the obtained mixture to form the required solid material. The manner of manufacturing process described above to form the mixture into the solid material is not intended to limit the scope of the present invention.
The solid material may be, for example, a flat sheet of material having a fixed geometric shape, such as a polygon of any one of a rectangle, square, circle, diamond, and triangle.
For example, the solid material can be formed by placing the mixed mixture in a mold, pressing the mixture with a suitable pressure, and hot pressing the mixture at a suitable temperature and for a period of time to cure the mixture until the surface hardness (Shore D hardness) distribution is in the range of 60 to 92. The pressure is generally 0.01 kg/cm2To 300 kg/cm2And the temperature is higher than room temperature. As for the longer the hot pressing time, the harder the resulting solid material.
In step 100, the waste phenolic aldehyde polymer material is crushed and powdered, and then soaked in an acidic or alkaline solution, so that the surface of the waste phenolic aldehyde polymer material is corroded or cracked into finer powder, and the main purpose of the method is to increase the solidification force of the resin in the subsequent steps. The acidic or alkaline solution includes but is not limited to aqueous solutions of strong acid, strong base, weak acid, weak base, etc., and may be but is not limited to acid-base aqueous solutions of hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid, aqua regia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous calcium hydroxide solution, aqueous magnesium hydroxide solution, etc. The weight concentration of the acidic or basic solution is in the concentration range of 0.1% to 99% aqueous solution.
For example, the powder of the waste phenolic polymer material is soaked in a proper amount of strong alkali sodium hydroxide solution (with the concentration of 10%, w/w), and the strong alkali sodium hydroxide solution submerges the powder surface of the waste phenolic polymer material to carry out surface destruction. After 2 days, the strong alkaline sodium hydroxide solution was drained and the waste phenolic polymeric material powder was cleaned with water to pH: after 7-9 deg.C, drying at 100 deg.C.
The present invention is a plate structure 1 with a specific geometric shape, which is mainly a plate structure 1 formed by mixing waste phenolic polymer material, wood fiber and resin, wherein the weight ratio of the waste phenolic polymer material powder to the wood fiber powder can be in the range of 0.01 to 0.99; wherein the weight ratio of the resin is more than 0.01. The plate structure 1 further comprises a bridging agent. Wherein the composition of each material is as described above. The plate structure 1 has a fixed geometrical shape, such as a polygon with various shapes, such as a rectangle or a square (as shown in fig. 2), a circle (as shown in fig. 3), a diamond (as shown in fig. 4), a triangle (as shown in fig. 5), and the like.
In the first embodiment of the present application example, the mixing ratio of the powder of the waste phenolic polymer material (i.e., the bakelite waste), the powder of the wood fiber and the resin (e.g., phenolic resin) in the step 130 is 1: 1: 1, and forming the solid material by applying a hot pressing manner in the above step 140, wherein a hot pressing pressure is 40 kgf/cm2The hot pressing temperature is 150 ℃, and the hot pressing time is 1 hour. Therefore, the solid material with a specific thickness can be obtained to be used as an environment-friendly bakelite phenolic material. Wherein the solid material has a surface hardness (Shore D hardness) distribution ranging from 60 to 92. The solid material may be formed as a flat sheet having a thickness of 2.5 mm and having a fixed geometric shape, such as a polygon of any one of a rectangle, square, circle, diamond, and triangle. The solid material can be used as a drilling plate in the printed circuit board industry, is a low-order environment-friendly drilling plate, or is a cutting protection plate when a copper foil substrate is cut.
In the second embodiment of the present application example, the mixing conditions of the powder of the waste phenolic polymeric material (i.e., the bakelite waste) and the powder of the wood fiber and the resin (e.g., the phenolic resin) in the step 130 are the same as those in the first embodiment (i.e., the mixing ratio by weight is 1: 1: 1), and the solid material is also formed by applying a hot pressing method in the step 140. But wherein the hot pressing pressure is 50 kgf/cm2The hot pressing temperature is 150 ℃, and the hot pressing time is 1 hour. Therefore, the solid material with a specific thickness can be obtained to be used as an environment-friendly bakelite phenolic material. Wherein the solid material has a surface hardness (Shore D hardness) distribution ranging from 70 to 90. The solid material may be formed as a flat sheet of 1.5 mm thickness having a fixed geometric shape, such as a polygon of any one of a rectangle, square, circle, diamond, and triangle. The solid material can be used as a drilling plate in the printed circuit board industry, is an intermediate-grade environment-friendly drilling plate, or is a cutting protection plate when a copper foil substrate is cut.
In the third example of the present application example, the waste phenol-formaldehyde condensate is polymerized in the step 130The mixing conditions of the powder of the composite material (i.e., the bakelite waste) and the powder of the wood fiber and the resin (e.g., the phenolic resin) are the same as those in the first embodiment (i.e., the mixing ratio by weight is 1: 1: 1). In step 140, the obtained mixture is placed in a mold, and the solid material is formed by applying a hot pressing method, wherein when the mixed mixture is placed in the mold, the bottom surface and the surface of the mold are respectively placed with a piece of glue-containing tissue (or commonly called a tissue film). Wherein the hot pressing pressure is 40 kgf/cm2The hot pressing temperature is 150 ℃, and the hot pressing time is 1 hour. Therefore, the solid material with a specific thickness can be obtained to be used as an environment-friendly bakelite phenolic material. Wherein the solid material has a surface hardness (Shore D hardness) distribution ranging from 85 to 95. The solid material can be made into a flat plate with a thickness of 1.5 mm, and has a fixed geometrical shape, such as a polygon with various shapes, such as rectangle, square, circle, rhombus, triangle, and the like. The solid material can be used as a drilling board in the printed circuit board industry and is regarded as a high-level environment-friendly drilling board.
In the fourth embodiment of the present application example, the mixing conditions of the powder of the waste phenolic polymeric material (i.e., the bakelite waste) and the powder of the wood fiber and the resin (e.g., the phenolic resin) in the step 130 are the same as those in the third embodiment (i.e., the mixing ratio by weight is 1: 1: 1), and the solid material is formed by applying a hot pressing method in the step 140. Wherein the hot pressing pressure is 50 kgf/cm2The hot pressing temperature is 150 ℃, and the hot pressing time is 1 hour. Therefore, the solid material with a specific thickness can be obtained to be used as an environment-friendly bakelite phenolic material. The solid material may have a surface hardness (Shore D hardness) distribution ranging from 85 to 95. The solid material can be made into a flat plate with a thickness of 3 mm, and has a fixed geometrical shape, such as a polygon of any one of rectangle, square, circle, diamond and triangle. The solid material can be used as a bakelite plate used in general industries and applied to jigs and clamps.
In a fifth embodiment of the present application example, in the step 130, the powder of the waste phenolic polymer material (i.e. the bakelite waste) in the first embodiment, the powder of the wood fiber and the resin (e.g. phenol) are mixedAldehyde resin) was changed to 1: 3: 2. wherein the particle size distribution of the powder of the waste phenolic polymer material and the powder of the wood fiber of the first embodiment is not changed, but the ratio of the used amount of the powder of the waste phenolic polymer material and the powder of the wood fiber is changed. The powder of the waste phenolic polymer material (namely the bakelite waste), the powder of the wood fiber and the resin (such as phenolic resin) are uniformly mixed by a homogenizer. In step 140, the resulting mixture is placed in a mold and hot pressing is applied to form the solid material. Wherein the hot pressing pressure is 30 kgf/cm2The hot pressing temperature is 150 ℃, and the hot pressing time is 1 hour. Therefore, the solid material with a specific thickness can be obtained to be used as an environment-friendly bakelite phenolic material. Wherein the solid material has a surface hardness (Shore D hardness) distribution ranging from 60 to 70. The solid material can be made into a flat plate with a thickness of 3 mm, and has a fixed geometrical shape, such as a polygon of any one of rectangle, square, circle, diamond and triangle. The solid material can be used as a fiber board of decorative materials.
In the sixth embodiment of the present application example, the mixing conditions of the powder of the waste phenolic polymeric material (i.e., the bakelite waste), the powder of the wood fiber and the resin (e.g., the phenolic resin) in the step 130 are the same as those in the fourth embodiment (i.e., the mixing ratio is 1: 1: 1 by weight). In step 140, the obtained mixture is placed in a mold, and the solid material is formed by applying a hot pressing method, wherein when the mixed mixture is placed in the mold, the bottom surface and the surface of the mold are respectively placed with a piece of glue-containing tissue (or commonly called a tissue film). Wherein the hot pressing pressure is 40 kgf/cm2The hot pressing temperature is 150 ℃, and the hot pressing time is 1 hour. Therefore, the solid material with a specific thickness can be obtained to be used as an environment-friendly bakelite phenolic material. Wherein the solid material has a surface hardness (Shore D hardness) distribution ranging from 60 to 70. The solid material can be made into a flat plate with a thickness of 3 mm, and has a fixed geometrical shape, such as a polygon with various shapes, such as rectangle, square, circle, diamond, triangle, and the like. The solid material can be used as decorative board containing cosmetic and indoor decoration materials.
The mode of hot pressing the mould in the above processes can be changed into the mode of plastic extrusion to extrude the waste phenolic polymer material. A board-like floor-type product is obtained.
The invention has the advantages that the phenolic aldehyde type waste (namely the bakelite waste) and other fiber materials (preferably waste fibers) are properly crushed and ground to specific particle sizes, and then are mixed uniformly in a specific powder mixing ratio, and are supplemented with the addition of resin in a specific resin mixing ratio, so that the defect problems caused by uneven distribution and weak structure can be easily caused after the addition of new resin when the waste bakelite waste is taken as the main raw material of a new finished product in the prior art. And the situation that the product strength is insufficient when the waste fiber is taken as a main structure in the prior art can be avoided. The invention further uses the traditional plastic material manufacturing method to manufacture the final environment-friendly bakelite phenolic material finished product, which can be applied to a drilling lower backing plate, an upper cover plate, a table top plate and a cutting backing plate used in the manufacture of the printed circuit board industry and the copper foil substrate industry, or can be applied to a novel environment-friendly bakelite plate by using a mode which is not limited to the mode commonly used by bakelite, such as a clamp, a jig, a heat insulation material and an insulating material. But not limited to, the board can also be used as a board for decoration construction, such as plywood, a wood core board, a particle board, a melamine board, a fiber board, a foam board, a floor board, etc.; or a board for furniture; or for the purposes of external wall heat preservation and the like, and is regarded as a novel phenolic aldehyde bakelite material or a regenerated wood or material. Or a regenerated material formed by common plastic manufacturing processes such as a mould, a jig, injection, extrusion and the like. In addition, the regenerated material has the characteristics of continuous and repeated reproduction and recycling by the process. Thereby effectively reducing the environmental load and prolonging the service life of the incinerator and the landfill.
The detailed description is specific to possible embodiments of the invention, but the embodiments are not intended to limit the scope of the invention, and equivalent implementations or modifications without departing from the technical spirit of the invention should be included in the scope of the invention.
Claims (16)
1. A method for manufacturing recycled and reused phenolic type waste materials and environment-friendly bakelite phenolic materials is characterized by comprising the following steps:
step A: crushing and powdering the waste phenolic aldehyde polymeric material to form powder;
and B: crushing and powdering wood fibers to form powder;
and C: then mixing the powder of the waste phenolic polymer material with the powder of the wood fiber, wherein the mixing weight ratio of the two is in the range of 0.01 to 0.99;
step D: then adding resin, and uniformly mixing the powder of the waste phenolic aldehyde polymeric material, the powder of the wood fiber and the resin, wherein the resin is mainly used for bonding the powder of the waste phenolic aldehyde polymeric material and the powder of the wood fiber;
step E: and (3) applying one of hot pressing, cold pressing, injection by an injection machine, extrusion by an extrusion machine or foaming to the obtained mixture to form the required solid material.
2. The method of claim 1, wherein in step a, the waste phenolic polymeric material is crushed, powdered, and then soaked in an acidic or alkaline solution to erode the surface of the waste phenolic polymeric material or break it down into fine powder.
3. A method according to claim 1 or 2, wherein the solid material is formed in step E by placing the mixed mixture in a mould, pressing with a suitable pressure, and curing at a suitable temperature for a period of time to a surface hardness distribution in the range of 60 to 92; wherein the pressure is 0.01 kg/cm2To 300 kg/cm2A range, and a temperature greater than room temperature; wherein the longer the hot pressing time, the harder the resulting solid material.
4. The method of claim 2, wherein the acidic or basic solution is selected from the group consisting of aqueous acid-base solutions of hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid, aqua regia, aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous calcium hydroxide, aqueous magnesium hydroxide, and the like.
5. The method according to claim 1 or 2, wherein after the resin is added in step D, a bridging agent is added to form a three-dimensional structure.
6. The method of claim 1 or 2, wherein the waste phenolic polymeric material is selected from the group consisting of bakelite waste, phenolic upper cover plates used in mechanical drilling processes in printed circuit board manufacturing, lower backing plates, table top plates, and trim protective backing plates used in trimming processes in copper foil substrate manufacturing.
7. A method according to claim 1 or 2, wherein the wood fibres are selected from the group consisting of underboards for mechanical drilling processes in printed circuit board manufacturing, waste wood pulp boards, environmental protection boards, decorative or furniture boards, fresh fibre sources, wood flour, wood chips or agricultural waste; when the wood fiber is agricultural waste, the wood fiber is selected from rice straw and bagasse.
8. The method of claim 1 or 2, wherein the resin is selected from the group consisting of phenolic resin, urea-formaldehyde resin, epoxy resin, acryl resin, and a mixture of the foregoing resins.
9. The method as claimed in claim 1 or 2, wherein in the step D, the mixing ratio of the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin is 1: 1: 1; wherein the solid material is formed in step E by applying a hot pressing method to the resulting mixture; wherein the hot pressing pressure is 40 kgf/cm2Hot pressing temperature is 150 ℃, and hot pressing time is 1 hour; the solid material is used as an environment-friendly bakelite phenolic material; wherein the solid material has a surface hardness distribution ranging from 60 to 92; the solid material is used as a drilling board in the printed circuit board industry, and is regarded as a low-order environment-friendly drilling board or a cutting protector in the cutting of a copper foil substrate industryAnd protecting the plate.
10. The method as claimed in claim 1 or 2, wherein in the step D, the mixing ratio of the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin is 1: 1: 1; wherein the solid material is formed in step E by applying a hot pressing method to the resulting mixture; wherein the hot pressing pressure is 50 kgf/cm2Hot pressing temperature is 150 ℃, and hot pressing time is 1 hour; the solid material is used as an environment-friendly bakelite phenolic material; wherein the solid material has a surface hardness distribution ranging from 70 to 90; the solid material is used as a drilling plate in the printed circuit board industry, and is regarded as an intermediate-order environment-friendly drilling plate or a cutting protection plate when a copper foil substrate is cut.
11. The method as claimed in claim 1 or 2, wherein in the step D, the mixing ratio of the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin is 1: 1: 1; the solid material is formed by laying the obtained mixture in a mould in a hot-pressing mode, and when the mixed mixture is laid in the mould, the bottom surface and the surface of the mould are respectively provided with glue-containing paper; wherein the hot pressing pressure is 40 kgf/cm2Hot pressing temperature is 150 ℃, and hot pressing time is 1 hour; the solid material is used as an environment-friendly bakelite phenolic material; wherein the solid material has a surface hardness distribution ranging from 85 to 95; the solid material is used as a drilling board in the printed circuit board industry and is regarded as a high-level environment-friendly drilling board.
12. The method as claimed in claim 1 or 2, wherein in the step D, the mixing ratio of the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin is 1: 1: 1; wherein the solid material is formed in step E by applying a hot pressing method to the resulting mixture; wherein the hot pressing pressure is 50 kgf/cm2Hot pressing temperature is 150 ℃, and hot pressing time is 1 hour; the solid material is used as an environment-friendly bakelite phenolic material; the surface hardness distribution range of the solid material is between 85 and 95; the solid materialThe product can be used as bakelite board, fixture and clamp.
13. The method as claimed in claim 1 or 2, wherein in the step D, the mixing ratio of the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin is 1: 3: 2; wherein in step E, the mixed mixture is laid in a mould, and the solid material is formed by applying a hot-pressing mode; wherein the hot pressing pressure is 30 kgf/cm2Hot pressing temperature is 150 ℃, and hot pressing time is 1 hour; the solid material is used as an environment-friendly bakelite phenolic material; wherein the solid material has a surface hardness (Shore D hardness) distribution ranging from 60 to 70; the solid material is used as a fiberboard for decorative materials.
14. The method as claimed in claim 1 or 2, wherein in the step D, the mixing ratio of the powder of the waste phenolic polymer material, the powder of the wood fiber and the resin is 1: 1: 1; wherein in step E, the mixed mixture is laid in a mould, and the solid material is formed by applying a hot-pressing mode; wherein, when the mixed mixture is laid in a mould, the bottom surface and the surface of the mould are respectively provided with glue-containing facial tissue; wherein the hot pressing pressure is 40 kgf/cm2Hot pressing temperature is 150 ℃, and hot pressing time is 1 hour; the solid material is used as an environment-friendly bakelite phenolic material; wherein the solid material has a surface hardness distribution ranging from 60 to 70; the solid material can be used as decorative board containing cosmetic and indoor decoration materials.
15. An environment-friendly bakelite phenolic structure is a flat plate structure with a specific geometric shape, and is characterized in that the environment-friendly bakelite phenolic structure is a thick flat plate with a fixed geometric shape, and the shape is a polygon selected from any one of rectangle, square, circle, diamond and triangle; the environment-friendly bakelite phenolic structure is a flat plate structure formed by mixing waste phenolic polymeric materials, wood fibers and resin; wherein the weight ratio of the powder of the waste phenolic polymeric material mixed with the powder of the wood fiber is in the range of 0.01 to 0.99; wherein the weight ratio of the resin is more than 0.01.
16. The environmentally friendly bakelite phenolic structure according to claim 15, further comprising a bridging agent in the slab structure.
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| CN202010832153.8A CN114075364A (en) | 2020-08-18 | 2020-08-18 | Method for manufacturing recycled and reused phenolic aldehyde type waste and environment-friendly bakelite phenolic aldehyde material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268182A (en) * | 1994-03-31 | 1995-10-17 | Matsushita Electric Works Ltd | Phenolic resin molding material |
| CN107312291A (en) * | 2017-06-13 | 2017-11-03 | 广西信和新合成材料有限公司 | The processing method that phenolaldehyde moulding compound waste recovery is utilized |
| TWM605524U (en) * | 2020-06-24 | 2020-12-21 | 蘇峙銘 | Environment-friendly bakelite phenolic structure made by recycling and reusing phenolic waste |
-
2020
- 2020-08-18 CN CN202010832153.8A patent/CN114075364A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268182A (en) * | 1994-03-31 | 1995-10-17 | Matsushita Electric Works Ltd | Phenolic resin molding material |
| CN107312291A (en) * | 2017-06-13 | 2017-11-03 | 广西信和新合成材料有限公司 | The processing method that phenolaldehyde moulding compound waste recovery is utilized |
| TWM605524U (en) * | 2020-06-24 | 2020-12-21 | 蘇峙銘 | Environment-friendly bakelite phenolic structure made by recycling and reusing phenolic waste |
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Application publication date: 20220222 |