CN110818930A - Preparation method of novel phenolic-group SMC (sheet molding compound) material - Google Patents

Preparation method of novel phenolic-group SMC (sheet molding compound) material Download PDF

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CN110818930A
CN110818930A CN201911138257.2A CN201911138257A CN110818930A CN 110818930 A CN110818930 A CN 110818930A CN 201911138257 A CN201911138257 A CN 201911138257A CN 110818930 A CN110818930 A CN 110818930A
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resin
phenolic
smc
stirring
paste
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金柏青
叶柏菊
刘海波
张萌萌
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Qingdao Victall Era New Material Co Ltd
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Qingdao Victall Era New Material Co Ltd
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2061/00—Use of condensation polymers of aldehydes or ketones or derivatives thereof, as moulding material
    • B29K2061/04—Phenoplasts
    • 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
    • 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
    • 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
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
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Abstract

The invention discloses a preparation method of a novel phenolic SMC material, belonging to the technical field of phenolic SMC new materials and comprising the following steps: (1) modifying resin; (2) mixing and stirring the powder; (3) preparing resin paste slurry; (4) PF-SMC preparation; (5) curing; (6) and (5) molding. The invention has the advantages that the air is not required to be exhausted during the mould pressing, the technical problems that the phenolic aldehyde SMC material in the industry needs to be exhausted, the surface quality of the material is poor, the strength of a product is low, large parts are difficult to mould pressing and the like are solved, the problem of environmental pollution caused by the exhaust is solved, the process defect of the phenolic aldehyde SMC material is thoroughly changed, the product quality is obviously improved, and the ecological environment is protected.

Description

Preparation method of novel phenolic-group SMC (sheet molding compound) material
Technical Field
The invention relates to the technical field of phenolic aldehyde SMC new materials, in particular to a preparation method of a novel phenolic aldehyde SMC material.
Background
Organic polymer materials are flammable and can generate smoke and toxic gases during combustion, so that the organic polymer materials are difficult to be applied in the flame retardant field. At present, only polyimide resin and phenolic FRP are organic polymer materials which can reach the standard of fireproof materials.
Phenolic resin is the synthetic resin which is the earliest and has wider application, however, the technical progress of the phenolic composite material is slow due to the limitation of poor manufacturability, and particularly the research and application of phenolic SMC and similar technologies are not mature. The phenolic SMC material process has the following defects:
1. the curing of the phenolic resin belongs to a condensation reaction type, and small molecules and water generated by reaction need to be removed, so that the phenolic SMC needs to exhaust gas during the die pressing, and the exhaust effect is difficult to meet the requirement of the die pressing of products, because the phenolic SMC changes along with the change of storage time and temperature, the die pressing parameters are changed, the yield is reduced, and the surface quality is poor.
2. Because of poor manufacturability and low product yield, the phenolic aldehyde is basically used for pressing small and medium-sized parts, and except for phenolic aldehyde prepreg cloth, there are few successful cases for pressing large phenolic aldehyde SMC parts.
3. The phenolic materials also contain harmful substances such as phenol, aldehyde and the like in moisture discharged by die pressing, and have adverse effects on the environment.
4. The phenolic aldehyde material has high process difficulty, low product qualification rate and low production efficiency, so that the manufacturing cost of the phenolic aldehyde composite material is much higher than that of the polyester material.
5. The uncertainty of the exhaust process results in that the gas cannot be completely removed, so that the mechanical properties of the product are low and unstable.
The phenolic resin generates condensation water in condensation reaction, water needs to be discharged during mould pressing, and the phenolic resin-based material has high production process difficulty, seriously influences product quality and has low product percent of pass due to the influence of various factors such as proportion, temperature, pressure, material paving mode, time, exhaust mode and the like, so that the development and application of the phenolic resin material are restricted.
Disclosure of Invention
The invention discloses a preparation method of a novel phenolic-group SMC material, aiming at solving the technical problems of high difficulty of mould pressing exhaust process, low product qualification rate, low production efficiency and the like in the production process of phenolic resin-based materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a novel phenolic-based SMC material comprises the following steps:
(1) modification of resins
Adding phenolic resin into a stirring tank, adding benzoxazine resin, epoxy resin, a coupling agent and a catalyst, adding a viscosity reducer and a liquid release agent during mixing, and mixing and stirring to obtain modified resin paste;
(2) powder mixing
Premixing ordinary portland cement and high-aluminate cement in a conical mixer, adding an inorganic filler, uniformly mixing, adding a water reducing agent, a coagulant and lithium carbonate in the mixing process, and mixing and stirring to obtain premixed powder;
(3) preparation of resin paste
Adding the premixed powder into modified resin paste, stirring and blending at a high speed in a high-speed dispersion machine, adding hollow glass beads and zinc stearate in the mixing process, and controlling the viscosity to be 20000-plus-30000 CPS to prepare resin paste slurry;
(4) PF-SMC preparation
Feeding the prepared resin paste slurry into an SMC (sheet molding compound) unit, adding magnesium oxide paste, color paste and reinforcing fibers, controlling the temperature of a rubber groove and a bed surface in the SMC unit to be 45-50 ℃, and preparing PF-SMC (phenolic SMC sheet);
(5) aging
Curing the prepared PF-SMC sheet;
(6) die pressing
And (4) carrying out mould pressing after curing to obtain the novel phenolic group SMC material.
As a further preference of the invention, in the step (1), the mass ratio of the phenolic resin, the benzoxazine resin and the epoxy resin is 50-70:30-20: 1-10;
the coupling agent is KH550, and the addition amount is 3-4% of the total amount of the phenolic resin, the benzoxazine resin and the epoxy resin;
the catalyst is imidazole, and the addition amount of the catalyst is 1 to 1.2 percent of the mass of the benzoxazine resin;
the viscosity reducer is one of VITAX2018, VITAX2012, BYK9065 and BYK9080, and the addition amount of the viscosity reducer is 4-5% of the total amount of the resin.
As a further preferable aspect of the present invention, in the step (2), the weight ratio of the ordinary portland cement to the high aluminate cement is 1: (1-3), the inorganic filler is aluminum hydroxide, magnesium hydroxide, calcium hydroxide and calcium carbonate, and the weight ratio of the modified resin paste to the inorganic filler is 100 (50-100);
the selected ordinary portland cement has the particle size of 6-35 mu m and the surface area of 12000cm2The grain diameter of the high aluminate cement is 1-3 mu m, and the surface area is 22000cm2/g。
According to the further optimization of the invention, in the step (2), the mass ratio of the added water reducing agent to the inorganic filler is (1-2): 100; the mass ratio of the added accelerating agent to the inorganic filler is (3-5): 100; the mass ratio of the added lithium carbonate to the inorganic filler is (0.01-0.03): 100.
As a further preferred aspect of the present invention, in the step (3), the stirring conditions of the high-speed disperser are controlled as follows: the stirring speed is 1200-1600 r/min, the stirring temperature is 45-50 ℃, and the stirring time is 30-40 min.
In the step (4), the reinforcing fibers are selected from one or more of carbon fibers, glass fibers, basalt fibers and high silica fibers, are chopped fibers, continuous fibers or mixed fibers, and the mass ratio of the added reinforcing fibers to the resin paste slurry is (20-60): 100; the mass ratio of the added magnesium oxide paste to the resin paste slurry is (3-4): 100; the mass ratio of the added color paste to the resin paste is (2-5): 100.
As a further preferred aspect of the present invention, in the step (6), the molding parameters are:
material prepressing: 3-5 Mpa;
pre-pressing time: 10-15 sec;
and (3) mould pressing pressure: 10-15 Mpa;
and (3) die pressing time: 1.5 min/mm;
and (3) mould pressing temperature: 145-150 ℃;
spreading area: not less than 75 percent.
The detailed description of the preparation method is as follows:
the inorganic filler is a blend of sulphoaluminate cement or high-alumina cement and ordinary portland cement, and mainly has the main functions of capturing condensation water released during the curing of the phenolic resin and then carrying out hydration reaction, so that the problem of exhausting in the mould pressing process is solved; in addition, the hardening speed of the cement can be improved, and the manufacturing cost can be reduced.
The accelerator is beneficial to accelerating the hydration reaction speed in the mould pressing period and quickly finishing the curing reaction.
The water reducing agent can also be used for regulating the hydration reaction speed.
The lithium carbonate can assist the accelerating agent to shorten the hydration reaction time, and experiments prove that even if the doping amount of the lithium salt is not more than 0.01 percent of the mass of the cement, the setting time of the cement can be shortened from 4 hours to 1 hour.
The reinforcing fiber is added in the SMC sheet preparation process, and the requirements of various fields on environment-friendly phenolic SMC with high flame retardance, low smoke density, high strength and the like can be met.
The silica micropowder is used to be matched with cement for hydration reaction, so that the conversion rate of the hydration reaction can be improved.
The coupling agent is used, so that the binding force of the surfaces of the materials of all the components in the composite system can be enhanced, and the physical and chemical properties of the product can be improved.
The viscosity reducer is used, so that the viscosity of slurry in a system can be reduced, and the permeability of the reinforcing fiber is ensured.
The phenolic resin is modified by using the modified material, and the physical and chemical properties of the system blending slurry are improved so as to meet different requirements of mechanical strength and functionality of products.
According to the invention, the curing condition is set according to the gelling time of the resin paste slurry, so that the quality stability of the phenolic-based SMC is ensured; and then according to the gelation time of the resin paste, setting mould pressing parameters to ensure the qualification rate of the mould pressing products.
The phenolic resin must use the high-activity phenolic resin containing carboxylic acid group as matrix, said resin can be thickened by using thickening agent, then one or two new resins with high crosslinking degree and containing no water are blended, and modified by blending so as to change the defect of poor manufacturability of phenolic SMC. In the blended resin system, the thickening phenolic resin keeps the technological characteristics of SMC, and ensures that the blended matrix has the thickening characteristic. In addition, the novel non-aqueous phenolic resin does not emit water molecules when being cured, the discharge proportion of the whole water molecules is reduced, in the actual production, the mixing proportion of the phenolic resin and the modified resin can be selected according to the specific requirements of the product, the phenolic resin can be thickened by magnesium oxide, the thickening is stable, the water content is less than 3 percent, and the viscosity is less than 2000 cps; solids content greater than 70%, polymerization rate: 90-100 sec.
Benzoxazine resins and novel polymers which allow the phenolic resins to form interpenetrating networks. In the blended resin, due to the existence of phenolic hydroxyl and ortho-para active hydrogen of the phenolic resin, the ring opening mechanism of an oxazine ring is changed, the oxazine ring is changed from thermal ring opening to active hydrogen ring opening, the oxazine ring opening is promoted, and the condensation reaction of the phenolic resin is promoted by the released heat. The novel phenolic aldehyde blended and modified SMC not only keeps the thickening characteristic of the original pure phenolic aldehyde, but also has more excellent fluidity than the original system, obviously reduces the air displacement and is suitable for the die pressing process for pressing large parts.
The high aluminate cement and aluminosilicate cement belong to hydraulic cement, the main component of the high aluminate cement is calcium aluminate, and the main component of the silicate cement is calcium silicate, which is a main component forming hydration reaction. Unlike the hydration reaction of ordinary cement, the hydration reaction in this system is carried out at high temperature and high pressure. Because no water is added, the normal cement-cement ratio can not be achieved, a hardened structure of pure cement can not be formed, because the water discharged during the solidification of the phenolic aldehyde is very little, the requirement of hydration reaction can not be met, the formed microstructure is loose, and the addition of the modified phenolic resin causes the change of the cement stone pore structure, thereby changing the physical property of cement hardening. The modified phenolic polymer forms a film with higher cohesive force among all the components of the cement, and the hydration reaction and the polymer film forming are carried out simultaneously to form an interpenetrating network structure in which the polymer film and the cement structure are mutually interwoven.
The cement particles are a mixture of a plurality of minerals, wherein the mixture comprises C3S, C2S, C3AC4AF and other components, wherein C3S accounts for more than 50% of the content of cement, C3S carries out hydration reaction on water generated in the curing process of phenolic resin to generate calcium silicate hydrate and calcium hydroxide, the hydration reaction at the stage is different from the reaction of the cement and the water in principle, and a polycarboxylic acid water reducing agent is added into the cement premix material to adjust the hydration reaction speed. The polycarboxylate superplasticizer is an anionic surfactant, and a hydrophilic group at one end of the polycarboxylate superplasticizer can dissociate to form cations, so that the hydrophilic group is negatively charged. Due to the dispersion effect of the water reducing agent, more cement particles are kept in a mutually isolated state, the reaction area of the cement particles is increased, and the initial hydration reaction speed is increased. The addition amount of the water reducing agent is 1 percent of the amount of the cement.
In order to further improve the flame retardant property of the novel phenolic resin SMC and the requirement of actual products, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, silica micropowder and the like can be optionally added, materials with lower requirements on flame retardant property and lower cost can be further added, calcium carbonate and the like can be further added, and materials such as hollow microspheres and the like can be further added if low-density materials are required. The powdery materials are mixed in a conical mixer and then added into a stirring tank, and are mixed with modified resin, and an internal release agent and the like are added, and the mixture is stirred at a high speed to prepare resin paste.
It should be noted that in the manufacturing process, essentially the equipment used to make the unsaturated polyester SMC can be used. However, due to the sensitivity of the phenolic resin paste to temperature, auxiliary heating facilities such as a stirring tank, a glue scraping tank, a gumming machine bed surface, a compactor and a conveying pipeline must be added with a heating facility to ensure that the temperature is between 45 ℃ and 50 ℃ so as to be beneficial to the impregnation of the fibers. Due to the formulation system, a variety of powdery materials are used, such as: the cement with two specifications also contains inorganic fillers such as aluminum hydroxide, magnesium hydroxide, silicon micropowder and the like. In order to improve the production efficiency and facilitate the operation, various powder materials are premixed in a conical mixer, and powdery cement additives are added together. Of course, if the throughput is low, the powder may be directly fed into the agitation tank without using a conical mixer.
In the blending modification process, due to the addition of the modified resin, the condensation reaction of the phenolic resin is reduced, namely the moisture in the reaction is correspondingly reduced, so that the air displacement is reduced, and the molding parameters of the phenolic SMC are easy to control. Compared with a phenolic resin, the novel blended phenolic molding material has higher mechanical property and excellent manufacturability; the matrix of the molded product is compact, can meet the design requirements better than the traditional single phenolic resin, breaks through the bottleneck restricting the development of phenolic SMC technology, can also apply the principle of the patent to the processes of phenolic BMC, phenolic prepreg and the like, greatly improves the physical and chemical properties and functionality of phenolic composite materials, and manufactures phenolic composite material products with high strength, high flame retardance, low density and low VOC, thereby widening the application field of phenolic materials. The phenolic SMC can be used for pressing large phenolic SMC parts, deep-cavity and thin-wall phenolic SMC products, such as large parts of roofs, wallboards, door upright cover plates and the like, and provides a new material with high flame retardance, high strength, low density and environmental protection for the fields of high-speed railways, automobiles, electric appliances, building materials, national defense industry and the like.
The beneficial effect of the invention is that,
1. in the preparation process of the novel phenolic aldehyde group SMC material, exhaust is not needed during mould pressing, so that the manufacturing process of the phenolic aldehyde group SMC material is fundamentally improved, and the product quality is improved;
2. the mold pressing does not need to exhaust, the ecological environment is optimized, no VOC is discharged, and the method is a green manufacturing process;
3. the mould pressing does not need to exhaust, so that the mould pressing process is simplified, and the production efficiency is improved;
4. the reinforced fiber material can also be applied to the production process of other phenolic materials so as to improve the process conditions, improve the production efficiency and reduce the manufacturing cost.
In conclusion, because the air is not required to be exhausted during the die pressing, the technical problems that the phenolic aldehyde SMC material needs to be exhausted in the industry, the surface quality of the material is poor, the strength of a product is low, large parts are difficult to be die-pressed and the like are overcome, the problem of environmental pollution caused by the exhaust is solved, the process defect of the phenolic molding material is thoroughly changed, the product quality is obviously improved, the ecological environment is protected, and the method has great significance for the development of the society.
Drawings
FIG. 1 is a schematic view of the process of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a novel phenolic-based SMC material comprises the following steps:
(1) modification of resins
Adding phenolic resin into a stirring tank, stirring for 5min, then adding benzoxazine resin, epoxy resin, a coupling agent and a catalyst, adding a viscosity reducer and a liquid release agent during mixing, and mixing and stirring to obtain the modified resin paste.
The mass ratio of the phenolic resin to the benzoxazine resin to the epoxy resin is 50-70:30-20: 1-10;
the coupling agent is KH550, and the addition amount of the coupling agent is 3-4% of the total amount of the phenolic resin, the benzoxazine resin and the epoxy resin;
the catalyst is imidazole, and the addition amount of the catalyst is 1 to 1.2 percent of the mass of the benzoxazine resin.
The viscosity reducer is one of VITAX2018, VITAX2012, BYK9065 and BYK9080, and the addition amount of the viscosity reducer is 4-5% of the total amount of the resin.
The blending modification aims at increasing the toughness of the material and improving the physical and chemical properties of the composite material in a convenient mode, and the blending modification aims at adding the modified material and not generating water in the reaction so as to reduce the exhaust amount of the system.
(2) Powder mixing
Premixing ordinary portland cement and high-aluminate cement in a conical mixer, adding an inorganic filler, uniformly mixing, adding a water reducing agent, a coagulant and lithium carbonate in the mixing process, and mixing and stirring to obtain premixed powder.
The weight ratio of the ordinary Portland cement to the high aluminate cement is 1: (1-3) the inorganic filler is aluminum hydroxide, magnesium hydroxide, calcium hydroxide and calcium carbonate, and the weight ratio of the modified resin paste to the inorganic filler is 100 (50-100).
The selected ordinary portland cement has the particle size of 6-35 mu m and the surface area of 12000cm2The grain diameter of the high aluminate cement is 1-3 mu m, and the surface area is 22000cm2/g。
The mass ratio of the added water reducing agent to the inorganic filler is (1-2) to 100; the mass ratio of the added accelerating agent to the inorganic filler is (3-5): 100; the mass ratio of the added lithium carbonate to the inorganic filler is (0.01-0.03): 100.
Setting and hardening of cement is a very complicated physical-chemical process, when cement particles meet water released by phenolic curing, hydrolysis and hydration reactions occur to become hydrates, the hydrates are mutually overlapped by multiple gravitations in a certain way to form a cement stone structure, and in fact, SMC molding of phenolic resin and cement is carried out at high temperature and high pressure, which is not completely the same as the hydration of conventional cement, because the hydration of conventional cement is carried out at a certain water-cement ratio, and the water in the molding environment is only water generated by the phenolic curing reaction, and the water is small in amount and excessive in cement.
(3) Preparation of resin paste
Adding the premixed powder into modified resin paste, stirring and blending at a high speed in a high-speed dispersion machine, adding hollow glass beads and zinc stearate in the mixing process, and controlling the viscosity to be 20000-30000CPS to prepare resin paste slurry.
The stirring conditions of the high-speed dispersion machine are controlled as follows: the stirring speed is 1200-1600 r/min, the stirring temperature is 45-50 ℃, and the stirring time is 30-40 min.
It should be pointed out that if the production capacity is small, the conical helical agitator is not needed to be used for premixing, various powder materials can be sequentially added into the stirring tank and uniformly stirred at a high speed, the stirring tank and the resin paste conveying pipeline need to be provided with heating and heat-preserving facilities, and the temperature is ensured to be controlled between 45 ℃ and 50 ℃.
(4) PF-SMC preparation
And (3) feeding the prepared resin paste slurry into an SMC (sheet molding compound) unit, adding magnesium oxide paste, color paste and reinforcing fibers, and controlling the temperature of a rubber groove and a bed surface in the SMC unit to be 45-50 ℃ to prepare the PF-SMC sheet.
Controlling the temperature of a rubber groove and a bed surface in an SMC unit to be 45-50 ℃, and scraping a clearance: 1.2mm-1.6 mm; the running speed of the unit is as follows: 8-18M/min, ensuring the permeability of the fiber and avoiding dry fiber.
If the colored material is manufactured, the phenolic aldehyde system color paste is also added, and the addition amount is 2 to 5 percent of the amount of the resin paste.
The fiber with different proportions is added according to the requirement of a product, the reinforced fiber can be designed according to the product, the reinforced fiber is one or more selected from carbon fiber, glass fiber, basalt fiber and high silica fiber, and is chopped fiber, continuous fiber or mixed fiber, various reinforced fibers can be cut into the specifications of 12.5mm, 25.4mm, 50.8mm and the like according to the requirement, and the fiber content is 20-60%.
(5) Aging
Curing the prepared PF-SMC sheet;
the curing parameters are set as follows:
curing temperature: 45-55 ℃;
curing time: 20-120 hours;
resin paste curing viscosity: 1500 to 3000 million cps.
(6) Die pressing
And (4) carrying out mould pressing after curing to obtain the novel phenolic group SMC material.
The molding parameters were set as:
material prepressing: 3-5 Mpa;
pre-pressing time: 10-15 sec;
and (3) mould pressing pressure: 10-15 Mpa;
and (3) die pressing time: 1.5 min/mm;
and (3) mould pressing temperature: 145-150 ℃;
spreading area: not less than 75 percent.
Application example
The preparation method of the novel phenolic aldehyde group SMC material has the advantages of high strength, high flame retardance, low smoke and low VOC, the material proportion in the production process is different for products with different shrinkage rates, and the material dosage in the typical five formulas is listed as follows.
Watch 1
Name of Material Formulation 1 Formulation 2 Formulation 3 Formulation 4 Formulation 5
Phenolic resin 60 70 80 100 60
Benzoxazine resins 40 30 20 - 30
Epoxy resin - - - - 10
Catalyst and process for preparing same 0.04 0.03 0.02 - 0.04
Coupling agent 4 4 4 4 4
Viscosity reducer 5 4.5 4 3 5
Hydrogen and oxygenAluminium alloy 2 2 2 2 2
Magnesium hydroxide 15 15 15 15 15
Zinc stearate 4.2 4..2 4.2 4.2 4.2
Portland cement 20 20 20 20 30
Silicon micropowder 15 15 15 15 10
High aluminate cement 40 40 40 40 50
Accelerating agent 2.4 2.4 2.4 2.4 2.5
Water reducing agent 0.6 0.6 0.6 0.6 0.8
Lithium carbonate 0.02 0.02 0.02 0.02 0.02
In the preparation process of the novel phenolic aldehyde group SMC material, the hydrophobic property after resin condensation reaction and the hydrophilic property of cement rehydration reaction are utilized, and exhaust is not needed during mould pressing, so that the preparation process of the phenolic aldehyde group mould pressing material is fundamentally improved, and the product quality is improved; the ecological environment is optimized, no VOC is discharged, the production efficiency is improved, and the method is a green manufacturing process.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.

Claims (8)

1. The preparation method of the novel phenolic aldehyde group SMC material is characterized by comprising the following steps:
(1) modification of resins
Adding phenolic resin into a stirring tank, adding benzoxazine resin, epoxy resin, a coupling agent and a catalyst, adding a viscosity reducer and a liquid release agent during mixing, and mixing and stirring to obtain modified resin paste;
(2) powder mixing
Premixing ordinary portland cement and high-aluminate cement in a conical mixer, adding an inorganic filler, uniformly mixing, adding a water reducing agent, a coagulant and lithium carbonate in the mixing process, and mixing and stirring to obtain premixed powder;
(3) preparation of resin paste
Adding the premixed powder into modified resin paste, stirring and blending at a high speed in a high-speed dispersion machine, adding hollow glass beads and zinc stearate in the mixing process, and controlling the viscosity to be 20000-plus-30000 CPS to prepare resin paste slurry;
(4) PF-SMC preparation
Feeding the prepared resin paste slurry into an SMC (sheet molding compound) unit, adding magnesium oxide paste, color paste and reinforcing fibers, and controlling the temperature of a rubber groove and a bed surface in the SMC unit to be 45-50 ℃ to prepare PF-SMC;
(5) aging
Curing the prepared PF-SMC sheet;
(6) die pressing
And (4) carrying out mould pressing after curing to obtain the novel phenolic group SMC material.
2. The method for preparing a novel phenolic-based SMC material as claimed in claim 1, wherein in step (1), the mass ratio of the phenolic resin, the benzoxazine resin and the epoxy resin is 50-70:30-20: 1-10;
the coupling agent is KH550, and the addition amount is 3-4% of the total amount of the phenolic resin, the benzoxazine resin and the epoxy resin;
the catalyst is imidazole, and the addition amount of the catalyst is 1 to 1.2 percent of the mass of the benzoxazine resin;
the viscosity reducer is one of VITAX2018, VITAX2012, BYK9065 and BYK9080, and the addition amount of the viscosity reducer is 4-5% of the total amount of the resin.
3. The method for preparing a novel phenolic-based SMC material as claimed in claim 1, wherein in step (2), the weight ratio of ordinary portland cement to high aluminate cement is 1: (1-3), the inorganic filler is aluminum hydroxide, magnesium hydroxide, calcium hydroxide and calcium carbonate, and the weight ratio of the modified resin paste to the inorganic filler is 100 (50-100);
the selected ordinary portland cement has the particle size of 6-35 mu m and the surface area of 12000cm2The grain diameter of the high aluminate cement is 1-3 mu m, and the surface area is 22000cm2/g。
4. The preparation method of the novel phenolic-based SMC material as claimed in claim 1, wherein in the step (2), the mass ratio of the added water reducing agent to the inorganic filler is (1-2): 100; the mass ratio of the added accelerating agent to the inorganic filler is (3-5): 100; the mass ratio of the added lithium carbonate to the inorganic filler is (0.01-0.03): 100.
5. The method for preparing a novel phenolic-based SMC material of claim 1, wherein in step (3), the stirring conditions of the high-speed disperser are controlled as follows: the stirring speed is 1200-1600 r/min, the stirring temperature is 45-50 ℃, and the stirring time is 30-40 min.
6. The preparation method of a novel phenolic-based SMC material as claimed in claim 1, wherein in step (4), the reinforcing fiber is one or more selected from carbon fiber, glass fiber, basalt fiber and high silica fiber, and is chopped fiber, continuous fiber or hybrid fiber, and the mass ratio of the added reinforcing fiber to the resin paste slurry is (20-60): 100; the mass ratio of the added magnesium oxide paste to the resin paste slurry is (3-4): 100; the mass ratio of the added color paste to the resin paste is (2-5): 100.
7. The method for preparing a novel phenolic-based SMC material of claim 1, wherein in step (5), the curing parameters are set as follows:
curing temperature: 45-55 ℃;
curing time: 20-120 hours;
resin paste curing viscosity: 1500 to 3000 million cps.
8. The method for preparing a novel phenolic-based SMC material of claim 1, wherein in step (6), the molding parameters are respectively:
material prepressing: 3-5 Mpa;
pre-pressing time: 10-15 sec;
and (3) mould pressing pressure: 10-15 Mpa;
and (3) die pressing time: 1.5 min/mm;
and (3) mould pressing temperature: 145-150 ℃;
spreading area: not less than 75 percent.
CN201911138257.2A 2019-11-20 2019-11-20 Preparation method of novel phenolic-group SMC (sheet molding compound) material Pending CN110818930A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542396A (en) * 2016-01-26 2016-05-04 广东汕头超声电子股份有限公司覆铜板厂 High-modulus epoxy resin composition, preparation method thereof, prepreg and laminated board manufactured from same and preparation method of prepreg and laminated board
CN105585821A (en) * 2016-01-26 2016-05-18 广东汕头超声电子股份有限公司覆铜板厂 Halogen-free resin composition, no-flow prepreg prepared from halogen-free resin composition and manufacturing method of prepreg
EP3252680A1 (en) * 2016-05-31 2017-12-06 Agfa Graphics NV Authentication method of a two dimensional bar code

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542396A (en) * 2016-01-26 2016-05-04 广东汕头超声电子股份有限公司覆铜板厂 High-modulus epoxy resin composition, preparation method thereof, prepreg and laminated board manufactured from same and preparation method of prepreg and laminated board
CN105585821A (en) * 2016-01-26 2016-05-18 广东汕头超声电子股份有限公司覆铜板厂 Halogen-free resin composition, no-flow prepreg prepared from halogen-free resin composition and manufacturing method of prepreg
EP3252680A1 (en) * 2016-05-31 2017-12-06 Agfa Graphics NV Authentication method of a two dimensional bar code

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Application publication date: 20200221