CN116041899A - Method for preparing ammonia-free phenolic moulding material by efficiently utilizing waste phenolic moulding material products - Google Patents
Method for preparing ammonia-free phenolic moulding material by efficiently utilizing waste phenolic moulding material products Download PDFInfo
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Abstract
The invention relates to the technical field of material preparation, in particular to a method for preparing ammonia-free phenolic injection molding materials by efficiently utilizing waste phenolic molding plastic products, which comprises the following raw materials in parts by weight: 20-35 parts of water-soluble thermosetting phenolic resin, 50-60 parts of phenolic molding compound waste product powder, 0-15 parts of flame retardant, 0.5-1.5 parts of lubricant, 0.5-1.5 parts of release agent, 0.5-1.5 parts of pigment, 0.5-2.0 parts of curing accelerator and 0-20 parts of glass fiber; the invention can efficiently utilize waste phenolic molding plastic parts, the utilization rate is not lower than 50 percent, and simultaneously, the ammonia-free phenolic molding plastic with low cost can be prepared, and the phenolic molding plastic can replace the traditional phenolic molding plastic to be applied to manufacturing of common electrical appliances, such as electrical appliance insulating components of switches, sockets, relay inserts, wire connectors, coil bobbins and the like.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a method for preparing ammonia-free phenolic injection molding materials by efficiently utilizing waste phenolic molding plastic products.
Background
Phenolic moulding materials are the general names of the types of plastics which take phenolic resin as a base material and wood powder and the like as fillers, and are one of the most important thermosetting plastics. Because of its excellent properties of high mechanical strength, toughness, wear resistance, stable size, corrosion resistance, electric insulation, etc., it can be widely used for manufacturing electric appliances and daily-use industrial products, etc. Phenolic moulding compounds are thermosetting plastics, and the biggest problem is that the phenolic moulding compounds cannot be directly recycled or degraded after being cured and shaped like common thermoplastic plastics. During the molding process of phenolic molding compounds, a large number of defective products and runner accessories can appear, and the treatment method of the waste materials is usually burying or burning, which causes huge resource waste and potential environmental pollution damage. Both the publication patents "CN110157147a" and "CN111363302a" propose methods for effectively utilizing these phenolic molding compounds "waste", but the amount of "waste" used is less than 15% of the total formulation, and the utilization efficiency is low.
On the other hand, as a high-performance phenolic injection molding material, the ammonia-free phenolic injection molding material does not use urotropine curing agent, so that trace components such as free ammonia, nitrogen-containing compounds and the like which are easy to cause corrosion of electric elements do not exist in the product, and the service lives of instruments and electric products can be prolonged; in addition, the ammonia-free injection molding material has better heat resistance and mechanical strength, has wide application in the fields of high-end electrical elements and other materials, and shows excellent comprehensive performance. Research on the process and performance of ammonia-free injection molding materials is becoming a bright spot in the industry.
Currently, the technology of ammonia-free injection molding materials in developed countries and regions is mature and is widely used in the market, such as ammonia-free injection molding materials with the trademark Bakelite R PF4109 by MOMENTIVE Co., USA; a series of ammonia-free phenolic injection molding material varieties developed by Sumitomo corporation, such as PM9630, PM9750, PM9823, and the like; ammonia-free varieties such as CP-J-8500B, CP-J-8700 and CP-J-8800 were developed by Hitachi chemical Co., ltd; ammonia-free varieties such as CY8610 and CY8612 were also developed by Pink Denko electric company; PMC-T200NA, PMC-T200HF, PMC-T220NA, etc. of Taiwan vinca synthetic resin Co., ltd. The ammonia-free phenolic molding materials are mainly applied to the fields of various microswitches, converters, transformer coil frameworks, automobile booster pistons, water pump parts, belt pulleys and the like with higher end, the price of the products is 2-5 times that of common phenolic molding materials, and the application of the ammonia-free phenolic molding materials to common electrical appliances is greatly limited by the price.
Disclosure of Invention
The invention aims to provide a method for preparing ammonia-free phenolic moulding plastic by efficiently utilizing waste phenolic moulding plastic products, so as to solve the problems that the recycling rate of the waste phenolic moulding plastic products is low and the application of the ammonia-free phenolic moulding plastic to common electrical products is greatly limited in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the method for preparing the ammonia-free phenolic injection molding material by efficiently utilizing the waste phenolic molding material product comprises the following raw materials in parts by weight: 20-35 parts of water-soluble thermosetting phenolic resin, 50-60 parts of phenolic molding compound waste product powder, 0-15 parts of flame retardant, 0.5-1.5 parts of lubricant, 0.5-1.5 parts of release agent, 0.5-1.5 parts of pigment, 0.5-2.0 parts of curing accelerator and 0-20 parts of glass fiber;
the method for preparing the ammonia-free phenolic injection molding material comprises the following specific steps:
s11: putting the fine powder of the phenolic molding plastic part, the flame retardant, the lubricant, the release agent, the pigment and the curing accelerator which are metered in proportion into a high-speed dispersing machine for high-speed dispersion for 15-20min, and bagging for standby after ensuring uniform material dispersion;
s12: putting the synthesized water-soluble phenolic resin into a horizontal kneading kettle, stirring the kneading kettle to rotate forward, starting the kneading kettle to stir for 60-90R/min, and putting the powder which is well dispersed in the step S11 at high speed;
s13: opening a steam valve of a kneading kettle jacket, introducing steam into the kneading kettle jacket, heating materials in the kettle to 60-65 ℃ at a heating rate of 2-3 ℃/min by controlling steam and cooling water, and carrying out grafting reaction for 45-90 min in the state; in this state, the thermosetting phenol resin prepolymer containing a large amount of methylol groups can be coated on the surface of the fine powder of the phenol molding plastic part by heating and stirring, and can penetrate into the fine holes of the fine powder, and simultaneously, the methylol groups in the thermosetting phenol resin prepolymer can undergo nucleophilic substitution or dehydration condensation reaction with the unreacted groups of the phenol resin in the fine powder, so that the phenol resin is grafted onto the fine powder particles;
s14: after the kneading reaction is finished, stirring the kneading kettle to be reversed, and discharging after reversing stirring for 5-10 min at the rotating speed of 60-90R/min;
s15: the materials are conveyed into a hopper of a mesh belt type oven through a dragon conveyor, are evenly paved on a mesh belt of the mesh belt type oven through a distributor, the thickness of the paved materials is controlled to be 4-8 cm, the advancing speed of the mesh belt is controlled to be 0.3-0.5 m/min, and the temperature of hot air in six areas of the mesh belt is respectively controlled to be: the first area is 100-110 ℃, and the second area is 110-120 ℃; the temperature of the third area is 110-120 ℃; the temperature of the fourth area is 100-110 ℃; five zones 80-90 ℃; the temperature of the six areas is 40-60 ℃; the drying time of the materials in the mesh belt oven is 100-170 min, and the water content of the outlet materials is 3-5% as qualified;
s16: the dried material is cooled to below 40 ℃ by air conveying and then is crushed by a high-speed crusher, the crushed material is ground by a ball mill for 2-3 hours, and then is sieved by a screen with 40-80 meshes to obtain phenolic molding material powder, and the phenolic molding material powder is packaged and then enters the next working procedure;
s17: putting the ball-milled powder into a horizontal blade stirrer according to a proportion, adjusting the rotating speed to 40-80 r/min, putting the glass fiber chopped filaments according to a proportion, and stirring and mixing for 20-40 min to enable the glass fiber chopped filaments to be uniformly dispersed in the powder material;
s18: starting a screw conveyor, adjusting the rotating speed of the screw conveyor to 20-40 r/min, adjusting the rotating speed of a horizontal blade stirrer to 5-15 r/min, opening a blanking valve of the horizontal blade stirrer, and conveying the mixed materials into a hopper of a metering screw by using the screw conveyor;
s19: when the material of the metering screw hopper reaches 2/3, starting a double-screw mixing extruder, and sequentially starting an oil pump, a main machine screw, a lateral feeder screw and the metering screw; before starting the host screw, the host screw needs to be preheated for at least 1h in advance, and the temperature of three areas is set: 60-80 ℃ in the first region, 90-110 ℃ in the second region and 110-130 ℃ in the third region;
s110: the rotational speeds of a main machine screw and a metering screw are slowly adjusted to 200r/min and 20r/min, and after materials are extruded and agglomerated from a double-screw mixing extruder, conveying and granulating equipment such as a tablet press, a belt conveyor, an air cooler, a crushing granulator, a vibrating screen and the like is started;
s111: starting a cooling water circulating pump, wherein the first area and the second area are cooled by adopting low-temperature water, the temperature of the cooling water is lower than 35 ℃, and the third area is cooled by adopting chilled water, and the water temperature is lower than 10 ℃; the water pressure is not lower than 0.8MPa, and the water quantity is intelligently controlled by an electromagnetic valve;
s112: observing the temperature of the materials in the third area of the screw of the main machine, wherein the temperature of the materials in the first area is controlled to be 60-80 ℃, the temperature of the materials in the second area is controlled to be 90-110 ℃, and the temperature of the materials in the third area is controlled to be 110-130 ℃; when the temperature of the materials in the three areas is stable, the rotation speeds of a main machine screw and a metering screw are slowly adjusted to 200-400 r/min and 20-40 r/min, the materials are produced according to the process, extruded by a double screw mixing extruder, pressed into tablets by a tablet pressing machine, conveyed and cooled by a belt conveyor, crushed by a crushing granulator, sieved by a vibrating screen and batched and mixed by a conical mixing barrel, and the low-cost ammonia-free phenolic injection molding prepared by using waste products of aldehyde molding compounds is obtained.
Preferably, the water-soluble thermosetting phenolic resin is self-made, the solid content of the water-soluble thermosetting phenolic resin is 40-50%, the viscosity of the water-soluble thermosetting phenolic resin is 100-500 cp (25 ℃), the number average molecular weight Mn is 200-500, and the hydroxymethyl content is more than or equal to 20%.
Preferably, the preparation method of the water-soluble thermosetting phenolic resin comprises the following specific steps:
s21, performing S21; adding 592 parts of melted phenol solution into a reaction kettle with a condensing reflux device, starting a stirrer, controlling the stirring rotation speed to be 80-120 r/min, and adding 30-60 parts of 50% potassium hydroxide aqueous solution and 5-10 parts of barium hydroxide; controlling the temperature of the materials in the reaction kettle to be 45-50 ℃, stirring for 10-15 minutes at the temperature, and slowly injecting 1725.1-2587.7 parts of 37% formaldehyde solution into the reaction kettle;
s22, performing S22; after 37% of formaldehyde is injected, adjusting a steam valve and a cooling water valve, heating the temperature of a system material to 60-65 ℃ at a heating rate of 5-6 ℃/min, reacting for 60-90 min at the temperature, slowly injecting 248 parts of molten phenol solution into the reaction kettle after heat preservation is finished, and adding 15-30 parts of 50% of potassium hydroxide aqueous solution;
s23, performing S23; regulating the valves of steam and cooling water, heating the material temperature of the system to 70-75 ℃ at a heating rate of 5-6 ℃/min, and preserving heat for reaction for 30-60 min; after the heat preservation is finished, slowly injecting a third batch of 160 parts of melted phenol solution into the reaction kettle, and then adding 10-20 parts of 50% potassium hydroxide aqueous solution;
s24, performing S24; controlling the temperature of the materials in the reaction kettle to be 70-75 ℃, reacting under the condition until the materials are in cloud and fog in water at 0 ℃, adding 5-10 parts of KH550 silane coupling agent, stirring for 5min, and cooling to 60 ℃ to obtain the water-soluble phenolic resin.
Preferably, the preparation method of the phenolic molding compound waste part fine powder comprises the following specific steps:
s31: cleaning and crushing recycled molding compound waste materials such as phenolic molding compound defective products, runner accessories and the like, and crushing the molding compound waste materials into 80-mesh full-through fine powder by a high-speed crusher or a jet mill, wherein the residual rate of the fine powder passing through a 100-mesh screen is not more than 5%, and the residual rate of the fine powder passing through a 150-mesh screen is not more than 20%;
s32: putting the fine powder passing through the screen mesh into a sieve of not less than 10m 3 Is mixed for 30-60min in a conical mixing barrel, and the material of each batch is controlled to be 6-8m 3 Between them.
S33: and putting the batched and mixed fine powder into a feed box of a track type box oven, baking for 3-6 hours at 120-150 ℃ to remove moisture and ammonia in the fine powder, and obtaining the fine powder of the waste products of the phenolic molding compound.
Preferably, the moisture in the fine powder of the waste phenolic molding compound is less than or equal to 3 percent, and the free ammonia mEAM is less than or equal to 0.02 percent, which is qualified.
Preferably, the flame retardant is halogen-free flame retardant, and one or more of aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and antimony trioxide are selected.
Preferably, the accelerator is one or more of magnesium hydroxide, magnesium oxide and calcium hydroxide; the release agent is one or more of stearic acid, zinc stearate, magnesium stearate, calcium stearate and EBS; the pigment is one or more of oil-soluble aniline black and carbon black.
Preferably, the lubricant is one or more selected from polyethylene glycol-1000, polyethylene glycol-4000, polypropylene glycol-1000, polypropylene glycol-4000, polypropylene glycol-330N, stearic acid complex ester, oleamide and erucamide, PE wax and diethylene glycol dibenzoate.
Preferably, the glass fibers are chopped strands of glass fibers having a filament diameter of 3-70um.
Preferably, the surface of the glass fiber is treated by a coupling agent, and the silane coupling agent adopts an epoxy silane coupling agent or an amino silane coupling agent.
Compared with the prior art, the invention has the beneficial effects that: the method for preparing the ammonia-free phenolic moulding plastic by efficiently utilizing the waste phenolic moulding plastic products can efficiently utilize the waste phenolic moulding plastic products, the utilization rate of the waste phenolic moulding plastic products is not lower than 50 percent, and meanwhile, the ammonia-free phenolic moulding plastic with low cost can be prepared. The invention also has the following benefits:
(1) The self-made water-soluble thermosetting phenolic resin has low viscosity, can effectively coat and permeate into particles of waste part fine powder of the phenolic molding compound, and can effectively infiltrate glass fibers;
(2) The self-made water-soluble thermosetting phenolic resin has high hydroxymethyl content, can realize heating and curing without adding curing agents such as urotropine and the like, has high curing speed, and does not release ammonia gas when the prepared phenolic injection molding material is cured and molded;
(3) The self-made water-soluble thermosetting phenolic resin has high hydroxymethyl content, and the hydroxymethyl can carry out nucleophilic substitution or dehydration condensation reaction with the unreacted groups of the phenolic resin in the waste phenolic molding plastic part fine powder through heating, kneading and stirring, so that the phenolic resin is grafted onto fine powder particles;
(4) The self-made water-soluble thermosetting phenolic resin is grafted through physical coating and chemical reaction, so that the waste phenolic molding plastic part fine powder is effectively connected into a whole, and the prepared ammonia-free phenolic molding plastic has good comprehensive performance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method for preparing the ammonia-free phenolic injection molding material by efficiently utilizing the waste phenolic molding material product comprises the following raw materials in parts by weight: 30 parts of water-soluble thermosetting phenolic resin, 50 parts of phenolic molding plastic waste part powder, 10 parts of flame retardant, 1 part of lubricant, 1 part of release agent, 1 part of pigment, 2 parts of curing accelerator and 5 parts of glass fiber;
the method for preparing the ammonia-free phenolic injection molding material comprises the following specific steps:
s11: putting the fine powder of the phenolic molding plastic part, the flame retardant, the lubricant, the release agent, the pigment and the curing accelerator which are metered in proportion into a high-speed dispersing machine for high-speed dispersion for 20min, and bagging for standby after ensuring uniform material dispersion;
s12: putting the synthesized water-soluble phenolic resin into a horizontal kneading kettle, stirring the kneading kettle to rotate forward, starting the kneading kettle to stir for 60R/min, and putting the powder which is well dispersed at high speed in the step S11;
s13: opening a steam valve of a kneading kettle jacket, introducing steam into the kneading kettle jacket, heating the materials in the kettle to 65+/-1 ℃ at a heating rate of 2-3 ℃/min by controlling steam and cooling water, and carrying out grafting reaction for 60min in the state; in this state, the thermosetting phenol resin prepolymer containing a large amount of methylol groups can be coated on the surface of the fine powder of the phenol molding plastic part by heating and stirring, and can penetrate into the fine holes of the fine powder, and simultaneously, the methylol groups in the thermosetting phenol resin prepolymer can undergo nucleophilic substitution or dehydration condensation reaction with the unreacted groups of the phenol resin in the fine powder, so that the phenol resin is grafted onto the fine powder particles;
s14: after the kneading reaction is finished, stirring the kneading kettle to be reversed, and discharging after reversing and stirring for 10min at the rotating speed of 60R/min;
s15: the materials are conveyed into a hopper of a mesh belt type oven through a dragon conveyor, are evenly paved on a mesh belt of the mesh belt type oven through a distributor, the thickness of the paved materials is controlled to be 5-6 cm, the advancing speed of the mesh belt is controlled to be 0.4m/min, and the temperature of hot air in six areas of the mesh belt is respectively controlled to be: 105+/-2 ℃ in the first region and 115+/-2 ℃ in the second region; three regions 120+/-2 ℃; four zone 105±2 ℃; five zones 85+/-2 ℃; six zones 50+/-2 ℃; the drying time of the material in the mesh belt oven is 125min, and the water content of the outlet material is 3% -4% as qualified;
s16: cooling the dried material to below 40 ℃ by air conveying, then crushing the material by a high-speed crusher, grinding the crushed material by a ball mill for 2 hours, sieving the ground material by a 60-mesh screen to obtain phenolic molding compound powder, and packaging the powder and then entering the next working procedure;
s17: putting the ball-milled powder into a horizontal blade stirrer according to a proportion, adjusting the rotating speed to 60r/min, putting the glass fiber chopped filaments according to a proportion, stirring and mixing for 30min, and uniformly dispersing the glass fiber chopped filaments in the powder material;
s18: starting a screw conveyor, adjusting the rotating speed of the screw conveyor to 30r/min, adjusting the rotating speed of a horizontal blade stirrer to 10r/min, opening a blanking valve of the horizontal blade stirrer, and conveying the mixed materials into a hopper of a metering screw by using the screw conveyor;
s19: when the material of the metering screw hopper reaches 2/3, starting a double-screw mixing extruder, and sequentially starting an oil pump, a main machine screw, a lateral feeder screw and the metering screw; before starting the host screw, the host screw needs to be preheated for at least 1h in advance, and the temperature of three areas is set: the first area is 70 ℃, the second area is 100 ℃, and the third area is 120 ℃;
s110: the rotational speeds of a main machine screw and a metering screw are slowly adjusted to 200r/min and 20r/min, and after materials are extruded and agglomerated from a double-screw mixing extruder, conveying and granulating equipment such as a tablet press, a belt conveyor, an air cooler, a crushing granulator, a vibrating screen and the like is started;
s111: starting a cooling water circulating pump, wherein the first area and the second area are cooled by adopting low-temperature water, the temperature of the cooling water is lower than 35 ℃, and the third area is cooled by adopting chilled water, and the water temperature is lower than 10 ℃; the water pressure is not lower than 0.8MPa, and the water quantity is intelligently controlled by an electromagnetic valve;
s112: observing the temperature of the materials in the third area of the screw of the main machine, wherein the temperature of the materials in the first area is controlled to be 70+/-2 ℃, the temperature of the materials in the second area is controlled to be 100+/-2 ℃, and the temperature of the materials in the third area is controlled to be 120+/-2 ℃; after the temperature of the materials in the three areas is stable, the rotation speeds of a main machine screw and a metering screw are slowly adjusted to 350r/min and 35r/min, the materials are produced according to the process, extruded by a double-screw mixing extruder, pressed by a sheet pressing machine, conveyed by a belt conveyor for cooling, crushed by a crushing granulator, screened by a vibrating screen and batched and mixed by a conical mixing barrel, and the low-cost ammonia-free phenolic injection molding prepared by using waste products of aldehyde molding compounds is obtained.
In this example, the water-soluble thermosetting phenolic resin was self-made, had a solids content of 45.2%, a viscosity of 280cp (25 ℃ C.), a number average molecular weight Mn of 380, and a hydroxymethyl content of 21.6%.
The preparation method of the water-soluble thermosetting phenolic resin comprises the following specific steps:
s21, performing S21; adding 592 parts of melted phenol solution into a reaction kettle with a condensing reflux device, starting a stirrer, controlling the stirring speed to be 90r/min, and adding 5 parts of barium hydroxide, namely 30 parts of 50% potassium hydroxide aqueous solution; controlling the temperature of the materials in the reaction kettle to be 50+/-1 ℃, stirring for 10 minutes at the temperature, and slowly injecting 2156.4 parts of 37% formaldehyde solution into the reaction kettle;
s22, performing S22; after 37% of formaldehyde is injected, adjusting a steam valve and a cooling water valve, heating the temperature of a system material to 60+/-1 ℃ at a heating rate of 5-6 ℃/min, reacting for 90min at the temperature, slowly injecting 248 parts of molten phenol solution into the reaction kettle after heat preservation is finished, and adding 20 parts of 50% of potassium hydroxide aqueous solution;
s23, performing S23; regulating the valves of steam and cooling water, heating the material temperature of the system to 70+/-1 ℃ at a heating rate of 5 ℃/min, and preserving heat for reaction for 45min; after the heat preservation is finished, slowly injecting a third batch of 160 parts of melted phenol solution into the reaction kettle, and adding 10 parts of 50% potassium hydroxide aqueous solution;
s24, performing S24; controlling the temperature of the materials in the reaction kettle to be 7+/-1 ℃, reacting under the condition until the materials are in cloud and fog in water at 0 ℃, adding 10 parts of KH550 silane coupling agent, stirring for 5min, and cooling to 60 ℃ to obtain the water-soluble phenolic resin.
Further, the preparation of the fine powder of the waste phenolic molding compound comprises the following specific steps:
s31: cleaning and crushing recycled molding compound waste materials such as phenolic molding compound defective products, runner accessories and the like, and crushing the molding compound waste materials into 80-mesh full-through fine powder by a high-speed crusher, wherein the residual rate of the fine powder passing through a 100-mesh screen is not more than 5%, and the residual rate of the fine powder passing through a 150-mesh screen is not more than 20%;
s32: the fine powder passing through the screen is added to 10m 3 Is mixed for 40min in a conical mixing barrel, and the material of each batch is controlled to be 6-8m 3 Between them.
S33: and putting the batched and mixed fine powder into a feed box of a track type box oven, baking for 5 hours at 130 ℃, and removing moisture and ammonia in the fine powder to obtain the fine powder of the waste phenolic molding plastic parts.
It is worth to say that the moisture in the waste fine powder of the phenolic molding plastic is less than or equal to 3 percent, and the free ammonia mEAM is less than or equal to 0.02 percent, which is qualified.
Specifically, the flame retardant is a halogen-free flame retardant, a mixture of aluminum hydroxide and magnesium hydroxide is selected, and the accelerator is a mixture of magnesium oxide and calcium hydroxide; the release agent is stearic acid and zinc stearate; the pigment is oil-soluble aniline black, the lubricant is a mixture of polyethylene glycol-1000 and polyethylene glycol-40000, the glass fiber is a glass fiber chopped strand, the length of the glass fiber chopped strand is 3mm, the diameter of a monofilament is 13um, the surface of the glass fiber is treated by a coupling agent, and the silane coupling agent is an epoxy silane coupling agent.
The performance index of the product of example 1 is as follows: injection molding density 1.47g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Injection molding of marking piecesTime 35s; bending strength sigma fm 95.7MPa; flexural modulus 7.89GPa; tensile strength 56.2MPa; notched impact strength a of simply supported beam cu 2.05KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Load heat distortion temperature T ff 1.8 167 ℃; tracking index PTI 175V; the electrical strength is 12.0KV/mm; UL flame retardant rating (2.0 mm) V0 rating; free ammonia m E AM 0.012％。
Example 2
The method for preparing the ammonia-free phenolic injection molding material by efficiently utilizing the waste phenolic molding material product comprises the following raw materials in parts by weight: 28 parts of water-soluble thermosetting phenolic resin, 55 parts of phenolic molding plastic waste part powder, 5 parts of flame retardant, 1.5 parts of lubricant, 1 part of release agent, 1 part of pigment, 1.5 parts of curing accelerator and 7 parts of glass fiber;
the method for preparing the ammonia-free phenolic injection molding material comprises the following specific steps:
s11: putting the fine powder of the phenolic molding plastic part, the flame retardant, the lubricant, the release agent, the pigment and the curing accelerator which are metered in proportion into a high-speed dispersing machine for high-speed dispersion for 20min, and bagging for standby after ensuring uniform material dispersion;
s12: putting the synthesized water-soluble phenolic resin into a horizontal kneading kettle, stirring the kneading kettle to rotate forward, starting the kneading kettle to stir for 90R/min, and putting the powder which is well dispersed at high speed in the step S11;
s13: opening a steam valve of a kneading kettle jacket, introducing steam into the kneading kettle jacket, heating materials in the kettle to 60+/-1 ℃ at a heating rate of 2-3 ℃/min by controlling steam and cooling water, and carrying out grafting reaction for 90min in the state; in this state, the thermosetting phenol resin prepolymer containing a large amount of methylol groups can be coated on the surface of the fine powder of the phenol molding plastic part by heating and stirring, and can penetrate into the fine holes of the fine powder, and simultaneously, the methylol groups in the thermosetting phenol resin prepolymer can undergo nucleophilic substitution or dehydration condensation reaction with the unreacted groups of the phenol resin in the fine powder, so that the phenol resin is grafted onto the fine powder particles;
s14: after the kneading reaction is finished, stirring the kneading kettle to be reversed, and discharging after reversing and stirring for 5min at the rotating speed of 90R/min;
s15: the materials are conveyed into a hopper of a mesh belt type oven through a dragon conveyor, are evenly paved on a mesh belt of the mesh belt type oven through a distributor, the thickness of the paved materials is controlled to be 4-5 cm, the advancing speed of the mesh belt is controlled to be 0.5m/min, and the temperature of hot air in six areas of the mesh belt is respectively controlled to be: 110+/-2 ℃ in the first region and 120+/-2 ℃ in the second region; three regions 120+/-2 ℃; four regions 110+ -2deg.C; five zones 90+/-2 ℃; 60+/-2 ℃ in six areas; the drying time of the materials in the mesh belt oven is 100min, and the water content of the outlet materials is 3% -4% as qualified;
s16: cooling the dried material to below 40 ℃ by air conveying, then crushing the material by a high-speed crusher, grinding the crushed material by a ball mill for 3 hours, sieving the ground material by a 80-mesh screen to obtain phenolic molding compound powder, and packaging the powder and then entering the next working procedure;
s17: putting the ball-milled powder into a horizontal blade stirrer according to a proportion, adjusting the rotating speed to 80r/min, putting the glass fiber chopped filaments according to a proportion, stirring and mixing for 20min, and uniformly dispersing the glass fiber chopped filaments in the powder material;
s18: starting a screw conveyor, adjusting the rotating speed of the screw conveyor to 35r/min, adjusting the rotating speed of a horizontal blade stirrer to 10r/min, opening a blanking valve of the horizontal blade stirrer, and conveying the mixed materials into a hopper of a metering screw by using the screw conveyor;
s19: when the material of the metering screw hopper reaches 2/3, starting a double-screw mixing extruder, and sequentially starting an oil pump, a main machine screw, a lateral feeder screw and the metering screw; before starting the host screw, the host screw needs to be preheated for at least 1h in advance, and the temperature of three areas is set: the first area is 80 ℃, the second area is 110 ℃, and the third area is 130 ℃;
s110: the rotational speeds of a main machine screw and a metering screw are slowly adjusted to 200r/min and 20r/min, and after materials are extruded and agglomerated from a double-screw mixing extruder, conveying and granulating equipment such as a tablet press, a belt conveyor, an air cooler, a crushing granulator, a vibrating screen and the like is started;
s111: starting a cooling water circulating pump, wherein the first area and the second area are cooled by adopting low-temperature water, the temperature of the cooling water is lower than 35 ℃, and the third area is cooled by adopting chilled water, and the water temperature is lower than 10 ℃; the water pressure is not lower than 0.8MPa, and the water quantity is intelligently controlled by an electromagnetic valve;
s112: observing the temperature of the materials in the third area of the main machine screw, wherein the temperature of the materials in the first area is controlled to be 80+/-2 ℃, the temperature of the materials in the second area is controlled to be 110+/-2 ℃, and the temperature of the materials in the third area is controlled to be 130+/-2 ℃; after the temperature of the materials in the three areas is stable, the rotation speeds of a main machine screw and a metering screw are slowly adjusted to 400r/min and 40r/min, the materials are produced according to the process, extruded by a double-screw mixing extruder, pressed by a sheet pressing machine, conveyed by a belt conveyor for cooling, crushed by a crushing granulator, screened by a vibrating screen and batched and mixed by a conical mixing barrel, and the low-cost ammonia-free phenolic injection molding prepared by using waste products of aldehyde molding compounds is obtained.
In this example, the water-soluble thermosetting phenolic resin was self-made, had a solids content of 44.3%, a viscosity of 230cp (25 ℃ C.), a number average molecular weight Mn of 310, and a hydroxymethyl content of 23.8%.
The preparation method of the water-soluble thermosetting phenolic resin comprises the following specific steps:
s21, performing S21; adding 592 parts of melted phenol solution into a reaction kettle with a condensing reflux device, starting a stirrer, controlling the stirring rotation speed to be 90r/min, and adding 40 parts of 50% potassium hydroxide aqueous solution and 5 parts of barium hydroxide; controlling the temperature of the materials in the reaction kettle to be 50+/-1 ℃, stirring for 15 minutes at the temperature, and slowly injecting 2415.6 parts of 37% formaldehyde solution into the reaction kettle;
s22, performing S22; after 37% of formaldehyde is injected, adjusting a steam valve and a cooling water valve, heating the temperature of a system material to 60+/-1 ℃ at a heating rate of 5-6 ℃/min, reacting for 60min at the temperature, slowly injecting 248 parts of molten phenol solution into the reaction kettle after heat preservation is finished, and adding 30 parts of 50% of potassium hydroxide aqueous solution;
s23, performing S23; regulating the valves of steam and cooling water, heating the material temperature of the system to 75+/-1 ℃ at a heating rate of 5-6 ℃/min, and preserving heat for reaction for 30min; after the heat preservation is finished, slowly injecting a third batch of 160 parts of melted phenol solution into the reaction kettle, and adding 10 parts of 50% potassium hydroxide aqueous solution;
s24, performing S24; controlling the temperature of the materials in the reaction kettle at 75+/-1 ℃, reacting under the condition until the materials are in cloud and fog in water at 0 ℃, adding 5 parts of KH550 silane coupling agent, stirring for 5min, and cooling to 60 ℃ to obtain the water-soluble phenolic resin.
Further, the preparation of the fine powder of the waste phenolic molding compound comprises the following specific steps:
s31: cleaning and crushing recycled molding compound waste materials such as phenolic molding compound defective products, runner accessories and the like, and crushing the molding compound waste materials into 80-mesh full-through fine powder by a high-speed crusher or a jet mill, wherein the residual rate of the fine powder passing through a 100-mesh screen is not more than 5%, and the residual rate of the fine powder passing through a 150-mesh screen is not more than 20%;
s32: the fine powder passing through the screen is added to 10m 3 Is mixed for 30min in a conical mixing barrel, and the material of each batch is controlled to be 6-8m 3 Between them.
S33: and putting the batched and mixed fine powder into a feed box of a track type box oven, baking for 6 hours at 120 ℃, and removing moisture and ammonia in the fine powder to obtain the fine powder of the waste phenolic molding plastic parts.
It is worth to say that the moisture in the waste fine powder of the phenolic molding plastic is less than or equal to 3 percent, and the free ammonia mEAM is less than or equal to 0.02 percent, which is qualified.
Specifically, the flame retardant is a halogen-free flame retardant, a mixture of aluminum hydroxide and magnesium hydroxide is selected, and the accelerator is a mixture of magnesium oxide and calcium hydroxide; the release agent is calcium stearate and EBS; the pigment is carbon black, the lubricant is a mixture of polypropylene glycol-4000, polypropylene glycol-330N and diethylene glycol dibenzoate, the glass fiber is a glass fiber chopped strand, the length of the glass fiber is 3mm, the diameter of a monofilament is 13um, the surface of the glass fiber is treated by a coupling agent, and the silane coupling agent is an epoxy silane coupling agent or an amino silane coupling agent.
The performance index of the product of example 2 is as follows: injection molding density 1.47g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The injection molding time of the marking piece is 35s; bending strength sigma fm 102.4MPa; flexural modulus 8.36GPa; tensile strength 60.5MPa; notched impact strength of simply supported beamDegree a cu 2.14KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Load heat distortion temperature T ff 1.8 173 ℃; tracking index PTI 175V; the electrical strength is 12.0KV/mm; UL flame retardant rating (2.5 mm) V0 rating; free ammonia m E AM 0.015％。
As can be seen from the above table, the method for preparing ammonia-free phenolic molding material by using waste phenolic molding material products can efficiently use waste phenolic molding material products, the utilization rate of the waste phenolic molding material products is not lower than 50%, and meanwhile, the ammonia-free phenolic molding material with low cost can be prepared. The invention also has the following benefits:
(1) The self-made water-soluble thermosetting phenolic resin has low viscosity, can effectively coat and permeate into particles of waste part fine powder of the phenolic molding compound, and can effectively infiltrate glass fibers;
(2) The self-made water-soluble thermosetting phenolic resin has high hydroxymethyl content, can realize heating and curing without adding curing agents such as urotropine and the like, has high curing speed, and does not release ammonia gas when the prepared phenolic injection molding material is cured and molded;
(3) The self-made water-soluble thermosetting phenolic resin has high hydroxymethyl content, and the hydroxymethyl can carry out nucleophilic substitution or dehydration condensation reaction with the unreacted groups of the phenolic resin in the waste phenolic molding plastic part fine powder through heating, kneading and stirring, so that the phenolic resin is grafted onto fine powder particles;
(4) The self-made water-soluble thermosetting phenolic resin is grafted through physical coating and chemical reaction, so that the waste phenolic molding plastic part fine powder is effectively connected into a whole, and the prepared ammonia-free phenolic molding plastic has good comprehensive performance.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The method for preparing the ammonia-free phenolic moulding plastic by efficiently utilizing the waste phenolic moulding plastic product is characterized by comprising the following steps of: the composite material is prepared from the following raw materials in parts by weight: 20-35 parts of water-soluble thermosetting phenolic resin, 50-60 parts of phenolic molding compound waste product powder, 0-15 parts of flame retardant, 0.5-1.5 parts of lubricant, 0.5-1.5 parts of release agent, 0.5-1.5 parts of pigment, 0.5-2.0 parts of curing accelerator and 0-20 parts of glass fiber;
the method for preparing the ammonia-free phenolic injection molding material comprises the following specific steps:
s11: putting the fine powder of the phenolic molding plastic part, the flame retardant, the lubricant, the release agent, the pigment and the curing accelerator which are metered in proportion into a high-speed dispersing machine for high-speed dispersion for 15-20min, and bagging for standby after ensuring uniform material dispersion;
s12: putting the synthesized water-soluble phenolic resin into a horizontal kneading kettle, stirring the kneading kettle to rotate forward, starting the kneading kettle to stir for 60-90R/min, and putting the powder which is well dispersed in the step S11 at high speed;
s13: opening a steam valve of a kneading kettle jacket, introducing steam into the kneading kettle jacket, heating materials in the kettle to 60-65 ℃ at a heating rate of 2-3 ℃/min by controlling steam and cooling water, and carrying out grafting reaction for 45-90 min in the state; in this state, the thermosetting phenol resin prepolymer containing a large amount of methylol groups can be coated on the surface of the fine powder of the phenol molding plastic part by heating and stirring, and can penetrate into the fine holes of the fine powder, and simultaneously, the methylol groups in the thermosetting phenol resin prepolymer can undergo nucleophilic substitution or dehydration condensation reaction with the unreacted groups of the phenol resin in the fine powder, so that the phenol resin is grafted onto the fine powder particles;
s14: after the kneading reaction is finished, stirring the kneading kettle to be reversed, and discharging after reversing stirring for 5-10 min at the rotating speed of 60-90R/min;
s15: the materials are conveyed into a hopper of a mesh belt type oven through a dragon conveyor, are evenly paved on a mesh belt of the mesh belt type oven through a distributor, the thickness of the paved materials is controlled to be 4-8 cm, the advancing speed of the mesh belt is controlled to be 0.3-0.5 m/min, and the temperature of hot air in six areas of the mesh belt is respectively controlled to be: the first area is 100-110 ℃, and the second area is 110-120 ℃; the temperature of the third area is 110-120 ℃; the temperature of the fourth area is 100-110 ℃; five zones 80-90 ℃; the temperature of the six areas is 40-60 ℃; the drying time of the materials in the mesh belt oven is 100-170 min, and the water content of the outlet materials is 3-5% as qualified;
s16: the dried material is cooled to below 40 ℃ by air conveying and then is crushed by a high-speed crusher, the crushed material is ground by a ball mill for 2-3 hours, and then is sieved by a screen with 40-80 meshes to obtain phenolic molding material powder, and the phenolic molding material powder is packaged and then enters the next working procedure;
s17: putting the ball-milled powder into a horizontal blade stirrer according to a proportion, adjusting the rotating speed to 40-80 r/min, putting the glass fiber chopped filaments according to a proportion, and stirring and mixing for 20-40 min to enable the glass fiber chopped filaments to be uniformly dispersed in the powder material;
s18: starting a screw conveyor, adjusting the rotating speed of the screw conveyor to 20-40 r/min, adjusting the rotating speed of a horizontal blade stirrer to 5-15 r/min, opening a blanking valve of the horizontal blade stirrer, and conveying the mixed materials into a hopper of a metering screw by using the screw conveyor;
s19: when the material of the metering screw hopper reaches 2/3, starting a double-screw mixing extruder, and sequentially starting an oil pump, a main machine screw, a lateral feeder screw and the metering screw; before starting the host screw, the host screw needs to be preheated for at least 1h in advance, and the temperature of three areas is set: 60-80 ℃ in the first region, 90-110 ℃ in the second region and 110-130 ℃ in the third region;
s110: the rotational speeds of a main machine screw and a metering screw are slowly adjusted to 200r/min and 20r/min, and after materials are extruded and agglomerated from a double-screw mixing extruder, conveying and granulating equipment such as a tablet press, a belt conveyor, an air cooler, a crushing granulator, a vibrating screen and the like is started;
s111: starting a cooling water circulating pump, wherein the first area and the second area are cooled by adopting low-temperature water, the temperature of the cooling water is lower than 35 ℃, and the third area is cooled by adopting chilled water, and the water temperature is lower than 10 ℃; the water pressure is not lower than 0.8MPa, and the water quantity is intelligently controlled by an electromagnetic valve;
s112: observing the temperature of the materials in the third area of the screw of the main machine, wherein the temperature of the materials in the first area is controlled to be 60-80 ℃, the temperature of the materials in the second area is controlled to be 90-110 ℃, and the temperature of the materials in the third area is controlled to be 110-130 ℃; when the temperature of the materials in the three areas is stable, the rotation speeds of a main machine screw and a metering screw are slowly adjusted to 200-400 r/min and 20-40 r/min, the materials are produced according to the process, extruded by a double screw mixing extruder, pressed into tablets by a tablet pressing machine, conveyed and cooled by a belt conveyor, crushed by a crushing granulator, sieved by a vibrating screen and batched and mixed by a conical mixing barrel, and the low-cost ammonia-free phenolic injection molding prepared by using waste products of aldehyde molding compounds is obtained.
2. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the water-soluble thermosetting phenolic resin is self-made, the solid content of the water-soluble thermosetting phenolic resin is 40-50%, the viscosity of the water-soluble thermosetting phenolic resin is 100-500 cp (25 ℃), the number average molecular weight Mn is 200-500, and the hydroxymethyl content is more than or equal to 20%.
3. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 2, which is characterized in that: the preparation method of the water-soluble thermosetting phenolic resin comprises the following specific steps:
s21, performing S21; adding 592 parts of melted phenol solution into a reaction kettle with a condensing reflux device, starting a stirrer, controlling the stirring rotation speed to be 80-120 r/min, and adding 30-60 parts of 50% potassium hydroxide aqueous solution and 5-10 parts of barium hydroxide; controlling the temperature of the materials in the reaction kettle to be 45-50 ℃, stirring for 10-15 minutes at the temperature, and slowly injecting 1725.1-2587.7 parts of 37% formaldehyde solution into the reaction kettle;
s22, performing S22; after 37% of formaldehyde is injected, adjusting a steam valve and a cooling water valve, heating the temperature of a system material to 60-65 ℃ at a heating rate of 5-6 ℃/min, reacting for 60-90 min at the temperature, slowly injecting 248 parts of molten phenol solution into the reaction kettle after heat preservation is finished, and adding 15-30 parts of 50% of potassium hydroxide aqueous solution;
s23, performing S23; regulating the valves of steam and cooling water, heating the material temperature of the system to 70-75 ℃ at a heating rate of 5-6 ℃/min, and preserving heat for reaction for 30-60 min; after the heat preservation is finished, slowly injecting a third batch of 160 parts of melted phenol solution into the reaction kettle, and then adding 10-20 parts of 50% potassium hydroxide aqueous solution;
s24, performing S24; controlling the temperature of the materials in the reaction kettle to be 70-75 ℃, reacting under the condition until the materials are in cloud and fog in water at 0 ℃, adding 5-10 parts of KH550 silane coupling agent, stirring for 5min, and cooling to 60 ℃ to obtain the water-soluble phenolic resin.
4. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the preparation method of the waste part fine powder of the phenolic molding compound comprises the following specific steps:
s31: cleaning and crushing recycled molding compound waste materials such as phenolic molding compound defective products, runner accessories and the like, and crushing the molding compound waste materials into 80-mesh full-through fine powder by a high-speed crusher or a jet mill, wherein the residual rate of the fine powder passing through a 100-mesh screen is not more than 5%, and the residual rate of the fine powder passing through a 150-mesh screen is not more than 20%;
s32: putting the fine powder passing through the screen mesh into a sieve of not less than 10m 3 Is mixed for 30-60min in a conical mixing barrel, and the material of each batch is controlled to be 6-8m 3 Between them;
s33: and putting the batched and mixed fine powder into a feed box of a track type box oven, baking for 3-6 hours at 120-150 ℃ to remove moisture and ammonia in the fine powder, and obtaining the fine powder of the waste products of the phenolic molding compound.
5. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 4, wherein the method comprises the following steps: the moisture in the fine powder of the waste phenolic molding compound is less than or equal to 3 percent, and the free ammonia mEAM is less than or equal to 0.02 percent and is qualified.
6. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the flame retardant is halogen-free flame retardant, and one or more of aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and antimony trioxide are selected.
7. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the promoter is one or more of magnesium hydroxide, magnesium oxide and calcium hydroxide; the release agent is one or more of stearic acid, zinc stearate, magnesium stearate, calcium stearate and EBS; the pigment is one or more of oil-soluble aniline black and carbon black.
8. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the lubricant is one or more selected from polyethylene glycol-1000, polyethylene glycol-4000, polypropylene glycol-1000, polypropylene glycol-4000, polypropylene glycol-330N, stearic acid complex ester, oleamide and erucamide, PE wax and diethylene glycol dibenzoate.
9. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the glass fiber is chopped glass fiber, and the diameter of a monofilament is 3-70um.
10. The method for preparing ammonia-free phenolic molding material by efficiently utilizing waste phenolic molding material products according to claim 1, wherein the method comprises the following steps: the surface of the glass fiber is treated by a coupling agent, and the silane coupling agent adopts an epoxy silane coupling agent or an amino silane coupling agent.
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