CN110157147B - Method for recycling and reusing phenolic moulding plastic waste - Google Patents
Method for recycling and reusing phenolic moulding plastic waste Download PDFInfo
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- CN110157147B CN110157147B CN201910449298.7A CN201910449298A CN110157147B CN 110157147 B CN110157147 B CN 110157147B CN 201910449298 A CN201910449298 A CN 201910449298A CN 110157147 B CN110157147 B CN 110157147B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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Abstract
The invention relates to the field of waste recycling, in particular to a method for recycling and reusing phenolic moulding plastic waste, which is used for producing phenolic moulding plastic, wherein the phenolic moulding plastic comprises the following materials in parts by weight: coating the surface with modified phenolic moulding plastic waste; a phenolic resin; a reinforcing fiber; an inorganic filler; a curing agent; an auxiliary agent; the materials are uniformly mixed, the mixed materials are sent into an open mill or an extruder, and the phenolic molding compound is obtained after plastication, tabletting, cooling and crushing. The invention has the beneficial effects that: the invention adopts the phenolic moulding plastic waste as the raw material to react with the phenolic resin waste water, formaldehyde and catalyst to obtain the phenolic moulding plastic waste with the surface coated and modified, and then the phenolic moulding plastic waste is proportioned and remolded into the phenolic moulding plastic product, and the prepared finished product has good mechanical property, improves the utilization rate of resources and reduces the environmental pollution.
Description
Technical Field
The invention relates to the field of waste recycling, in particular to a method for recycling and reusing phenolic moulding plastic waste.
Background
Phenolic molding compounds (commonly known as bakelite powder) are the most long-standing plastics in the world, and are a general term for plastics based on phenolic resins, and the most important class of thermosetting plastics. It has excellent mechanical strength, toughness, wear resistance, stable size, corrosion resistance, electric insulation and other excellent performance, so that it is used in making electric appliance, daily use industrial product, etc. With the increase of the yield of the phenolic molding compound, a plurality of problems follow, wherein the biggest problem is the treatment problem of defective products and leftover materials (generally called waste materials) of the products, and the data show that 5% -7% of defective products are generated in the phenolic plastic processing process, and the defective products and the leftover materials after the phenolic molding compound is formed are generally treated by burying or burning. Burying the method requires a large amount of capital for treatment and causes long-term pollution to the environment; the incineration needs to consume more fuel, and more smoke dust and harmful gas are easily generated, so the two traditional treatment methods are infeasible from capital and new energy conservation and consumption reduction, the phenolic resin can generate wastewater in the production process, the wastewater mainly contains high-concentration phenol formaldehyde, the direct treatment not only needs higher sewage treatment cost, but also wastes the phenol formaldehyde in the wastewater, and therefore, the search for a recovery treatment method which can treat both the waste materials and the wastewater is imperative.
The Chinese patent with the patent number ZL03136165.X discloses a method for recovering phenolic moulding plastic waste, which directly mixes and heats crushed and refined phenolic moulding plastic waste with raw materials, then produces glue, cools and granulates. The Chinese patent with publication number CN201310112306.1 discloses a method for recycling fine powder of phenolic molding compound finished products, which comprises adding phenolic resin and glass fiber into the recycled fine powder of phenolic molding compound finished products, mixing at high speed, adding into a screw extruder to extrude powder, tabletting, cooling, pulverizing and screening. Chinese patent publication No. CN201710035773.7 discloses a method for recovering phenolic plastic waste, which comprises putting crushed material of phenolic plastic waste, curing agent, coupling agent and auxiliary agent into stirring equipment, mixing uniformly, transferring into a mold, performing hot-pressing treatment, cooling, and demolding to obtain phenolic products. The disclosed methods are all that the waste phenolic plastics is crushed and directly mixed with various raw materials to form a mold, and then the mold is directly used as a finished product, only the waste phenolic molding plastics can be recycled, and the problems of waste water in the production of phenolic resin and raw material recycling in the waste water cannot be solved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention aims to provide a method for recycling and reusing phenolic moulding plastic waste, which solves the technical problems of waste water in phenolic resin production and raw material recycling in the waste water.
The invention provides a method for recycling and reusing phenolic moulding plastic waste, which is used for producing phenolic moulding plastic, wherein the phenolic moulding plastic comprises the following materials in parts by weight:
uniformly mixing the materials, feeding the mixed materials into an open mill or an extruder, plasticating, tabletting, cooling and crushing to obtain the phenolic molding compound;
the preparation method of the phenolic molding plastic waste with the surface coated and modified comprises the following steps:
(1) crushing the phenolic molding plastic waste to obtain crushed materials;
(2) adding phenolic resin wastewater, crushed materials, formaldehyde and a catalyst into a reaction kettle;
(3) stirring and heating to 90-100 ℃, and stirring for reaction for 2-12 h;
(4) standing and precipitating for 1-10h, and discharging resin from the bottom of the reaction kettle;
(5) and dehydrating the resin discharged from the bottom to obtain the surface-coated modified crushed material, namely the surface-coated modified phenolic molding plastic waste material.
Further, in the method for recycling and reusing the waste phenolic molding plastic, the phenolic resin waste water is: wastewater produced by dehydration in the production of phenolic resin.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the catalyst is one or more of oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and the dosage of the catalyst is 0.1-1% of that of the phenolic resin wastewater.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the consumption of the crushed material is 1-10% of the consumption of the phenolic resin waste water, and the consumption of the formaldehyde is 0.5-5% of the consumption of the phenolic resin waste water.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the plastication temperature is 80-150 ℃.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the phenolic resin is one or two of thermoplastic phenolic resin or thermosetting phenolic resin.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the inorganic filler is selected from one or more of calcium carbonate, talcum powder, mica powder, wollastonite powder, white carbon black, magnesium oxide, calcium oxide and asbestos powder.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the curing agent is selected from one or more of hexamethylenetetramine, paraformaldehyde and p-toluenesulfonic acid.
Further, in the method for recycling and reusing the phenolic molding plastic waste, the auxiliary agent is one or more selected from titanate coupling agent, aluminate coupling agent, silane coupling agent, borate coupling agent, phosphate coupling agent, EBS, zinc stearate and calcium stearate.
Further, in the method for recycling and reusing the phenolic moulding plastic waste, the reinforcing fiber is selected from one or more of carbon fiber, basalt fiber, polyester fiber, alumina fiber, wood powder, paper powder, bamboo powder and glass fiber.
The invention has the beneficial effects that: the method comprises the steps of crushing the phenolic moulding plastic waste, putting the crushed waste as a raw material into a reaction kettle to react with phenolic resin wastewater, formaldehyde and a catalyst to obtain the phenolic moulding plastic waste with the surface coated and modified, and then proportioning and remolding the phenolic moulding plastic waste into a phenolic moulding plastic product, wherein the prepared finished product has good mechanical properties.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The invention provides a method for recycling and reusing phenolic moulding plastic waste, which is used for producing phenolic moulding plastic, wherein the phenolic moulding plastic comprises the following materials in parts by weight:
2 parts by weight of surface-coated modified phenolic moulding plastic waste;
35 parts by weight of thermoplastic phenolic resin;
20 parts by weight of carbon fibers;
5 parts by weight of calcium carbonate;
10 parts of hexamethylene tetramine;
1 part by weight of titanate coupling agent;
uniformly mixing the materials, feeding the mixed materials into an open mill or an extruder, plasticating, tabletting, cooling and crushing to obtain the phenolic molding compound; the temperature of the mastication was 80 ℃.
The preparation method of the phenolic molding plastic waste with the surface coated and modified comprises the following steps:
(1) crushing the phenolic molding plastic waste to obtain crushed materials;
(2) adding 100 parts of phenolic resin wastewater, 1 part of crushed material, 0.5 part of formaldehyde and 0.1 part of catalyst into a reaction kettle; the phenolic resin wastewater is wastewater produced by dehydration of phenolic resin production. The catalyst is oxalic acid;
(3) stirring and heating to 90-100 ℃, and stirring for reaction for 2-12 h;
(4) standing and precipitating for 1-10h, and discharging resin from the bottom of the reaction kettle;
(5) and dehydrating the resin discharged from the bottom to obtain the surface-coated modified crushed material, namely the surface-coated modified phenolic molding plastic waste material.
The other technical scheme provided by the invention is as follows: the method for recycling and reusing the waste phenolic molding compound is characterized in that the waste phenolic molding compound is used for producing the phenolic molding compound, and the phenolic molding compound is prepared from the following materials in parts by weight:
10 parts by weight of surface-coated modified phenolic moulding plastic waste;
40 parts by weight of thermosetting phenolic resin;
35 parts of basalt fibers;
10 parts of talcum powder;
20 parts of paraformaldehyde;
5 parts by weight of an aluminate coupling agent;
uniformly mixing the materials, feeding the mixed materials into an open mill or an extruder, plasticating, tabletting, cooling and crushing to obtain the phenolic molding compound; the temperature of the mastication was 150 ℃.
The preparation method of the phenolic molding plastic waste with the surface coated and modified comprises the following steps:
(1) crushing the phenolic molding plastic waste to obtain crushed materials;
(2) adding 100 parts of phenolic resin wastewater, 10 parts of crushed material, 5 parts of formaldehyde and 1 part of catalyst into a reaction kettle; the phenolic resin wastewater comprises the following components: wastewater produced by dehydration in the production of phenolic resin. The catalyst is one or more of oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acid, benzenesulfonic acid and p-toluenesulfonic acid;
(3) stirring and heating to 90-100 ℃, and stirring for reaction for 2-12 h;
(4) standing and precipitating for 1-10h, and discharging resin from the bottom of the reaction kettle;
(5) and dehydrating the resin discharged from the bottom to obtain the surface-coated modified crushed material, namely the surface-coated modified phenolic molding plastic waste material.
Examples 1 to 5
A preparation method of phenolic molding plastic waste with surface coating modification comprises the following steps:
(1) crushing: crushing the phenolic molding plastic waste to obtain crushed materials;
(2) adding phenolic resin wastewater, crushed materials, formaldehyde and oxalic acid (the specific raw materials of the surface coating modified phenolic molding compound of the examples 1-5 are shown in the table 1) into a reaction kettle;
(3) stirring and heating to 95 ℃, and stirring for reaction for 10 hours;
(4) standing and precipitating for 8h, and discharging resin from the bottom of the reaction kettle;
(5) and dehydrating the resin discharged from the bottom to obtain the surface-coated modified crushed material, namely the surface-coated modified phenolic molding plastic waste material.
TABLE 1 concrete raw material ratio of surface-coated modified phenolic moulding plastic
Examples 6 to 11
A method for recycling and reusing phenolic moulding plastic waste comprises the following steps:
uniformly mixing the surface-coated modified phenolic molding plastic waste (phenolic molding plastic proportioning amount is shown in the following table 2) obtained in the above examples 1-5, 37 parts of thermoplastic phenolic resin, 30 parts of reinforcing fiber, 8 parts of inorganic filler, 18 parts of hexamethylenetetramine and 2 parts of auxiliary agent, raising the temperature of an open mill to 120 ℃, feeding the mixed material into the open mill or an extruder, plasticating, tabletting, cooling and crushing to obtain phenolic molding plastic;
TABLE 2 phenolic moulding compound ratio
TABLE 3 comparison of phenolic moulding compound properties
As shown in the comparison table of the properties of the phenolic molding compound in Table 3, the phenolic molding compound prepared by recycling the phenolic resin produced by the waste water has better stability and mechanical properties under the same raw materials, proportioning and process conditions, and all the properties can meet the use standards.
In conclusion, the method for recycling and reusing the phenolic moulding plastic waste provided by the invention has the advantages that the phenolic moulding plastic is crushed and then is put into a reaction kettle to react with the phenolic resin waste water, formaldehyde and a catalyst to obtain the phenolic moulding plastic waste with the surface coated and modified, and then the phenolic moulding plastic waste is proportioned and remolded into the phenolic moulding plastic product, so that the prepared finished product has good mechanical property.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (8)
1. The method for recycling and reusing the waste phenolic molding compound is characterized in that the waste phenolic molding compound is used for producing the phenolic molding compound, and the phenolic molding compound comprises the following materials in parts by weight:
2-10 parts of surface-coated modified phenolic moulding plastic waste;
35-40 parts of phenolic resin;
20-35 parts of reinforcing fiber;
5-10 parts of inorganic filler;
10-20 parts of curing agent;
1-5 parts of an auxiliary agent;
uniformly mixing the materials, feeding the mixed materials into an open mill or an extruder, plasticating, tabletting, cooling and crushing to obtain the phenolic molding compound;
the preparation method of the phenolic molding plastic waste with the surface coated and modified comprises the following steps:
(1) crushing the phenolic molding plastic waste to obtain crushed materials;
(2) adding phenolic resin wastewater, crushed materials, formaldehyde and a catalyst into a reaction kettle;
(3) stirring and heating to 90-100 ℃, and stirring for reaction for 2-12 h;
(4) standing and precipitating for 1-10h, and discharging resin from the bottom of the reaction kettle;
(5) dehydrating the resin discharged from the bottom to obtain surface-coated modified crushed materials, namely the surface-coated modified phenolic molding plastic waste materials;
the phenolic resin wastewater comprises the following components: wastewater produced by dehydration in phenolic resin production;
the auxiliary agent is selected from one or more of titanate coupling agent, aluminate coupling agent, silane coupling agent, borate coupling agent, phosphate coupling agent, EBS, zinc stearate and calcium stearate.
2. The method for recycling and reusing the phenolic molding plastic waste material as claimed in claim 1, wherein the catalyst is one or more of oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and the amount of the catalyst is 0.1-1% of the amount of the phenolic resin waste water.
3. The method for recycling and reusing the phenolic molding compound waste material as claimed in claim 1, wherein the amount of the crushed material is 1-10% of the amount of the phenolic resin waste water, and the amount of the formaldehyde is 0.5-5% of the amount of the phenolic resin waste water.
4. The method of claim 1, wherein the temperature of the mastication is from 80 ℃ to 150 ℃.
5. The method of claim 1, wherein the phenolic resin is one or both of a thermoplastic phenolic resin and a thermosetting phenolic resin.
6. The method for recycling and reusing the phenolic molding compound waste material as claimed in claim 1, wherein the inorganic filler is selected from one or more of calcium carbonate, talc, mica powder, silica fume, silica white, magnesium oxide, calcium oxide and asbestos powder.
7. The method of claim 1, wherein the curing agent is one or more selected from the group consisting of hexamethylenetetramine, paraformaldehyde, and p-toluenesulfonic acid.
8. The method for recycling and reusing the phenolic molding compound waste material as claimed in claim 1, wherein the reinforcing fiber is selected from one or more of carbon fiber, basalt fiber, polyester fiber, alumina fiber, wood flour, paper flour, bamboo flour and glass fiber.
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| CN116041899A (en) * | 2022-12-21 | 2023-05-02 | 开化瑞达塑胶科技有限公司 | Method for preparing ammonia-free phenolic moulding material by efficiently utilizing waste phenolic moulding material products |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454766A (en) * | 2003-05-16 | 2003-11-12 | 林良菽 | Phenolic moulding composition waste matter treating and processing method |
| JP2006233141A (en) * | 2005-02-28 | 2006-09-07 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| CN106832753A (en) * | 2017-01-17 | 2017-06-13 | 湖北爱仕达电器有限公司 | A kind of phenoplasts waste material recovery method |
| 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 |
| CN109486101A (en) * | 2018-11-27 | 2019-03-19 | 江苏中鹏新材料股份有限公司 | Recoverying and utilizing method without ammonia phenolaldehyde moulding compound fine powder |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454766A (en) * | 2003-05-16 | 2003-11-12 | 林良菽 | Phenolic moulding composition waste matter treating and processing method |
| JP2006233141A (en) * | 2005-02-28 | 2006-09-07 | Sumitomo Bakelite Co Ltd | Phenolic resin molding material |
| CN106832753A (en) * | 2017-01-17 | 2017-06-13 | 湖北爱仕达电器有限公司 | A kind of phenoplasts waste material recovery method |
| 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 |
| CN109486101A (en) * | 2018-11-27 | 2019-03-19 | 江苏中鹏新材料股份有限公司 | Recoverying and utilizing method without ammonia phenolaldehyde moulding compound fine powder |
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Denomination of invention: A recycling and reusing method of phenolic molding compound waste Effective date of registration: 20220520 Granted publication date: 20220208 Pledgee: Agricultural Bank of China Limited Shaxian sub branch Pledgor: SHAXIAN HONGSHENG PLASTIC Co.,Ltd. Registration number: Y2022350000055 |
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Date of cancellation: 20221010 Granted publication date: 20220208 Pledgee: Agricultural Bank of China Limited Shaxian sub branch Pledgor: SHAXIAN HONGSHENG PLASTIC Co.,Ltd. Registration number: Y2022350000055 |
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Denomination of invention: A Method for Recycling and Reusing Phenolic Moulding Plastic Waste Effective date of registration: 20230928 Granted publication date: 20220208 Pledgee: Agricultural Bank of China Limited Sanming Sha County Branch Pledgor: SHAXIAN HONGSHENG PLASTIC Co.,Ltd. Registration number: Y2023350000211 |
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