CN113831822A - Method for manufacturing high-performance polyurea composite material - Google Patents
Method for manufacturing high-performance polyurea composite material Download PDFInfo
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- CN113831822A CN113831822A CN202110782258.1A CN202110782258A CN113831822A CN 113831822 A CN113831822 A CN 113831822A CN 202110782258 A CN202110782258 A CN 202110782258A CN 113831822 A CN113831822 A CN 113831822A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing a high-performance polyurea composite material, which is characterized in that slurry consists of A, B, C three components, wherein the component A consists of isocyanate; adding the liquid amine chain extender, the polyaspartic ester, the pigment, the anti-settling agent, the leveling agent and the auxiliary agent of the component B into a mixing kettle in a certain molar ratio or/and mass percentage and a certain feeding sequence, and mixing to obtain a component D mixture under the condition of a certain stirring speed; then mixing the main components of the component A and the component D into polyurea slurry in a ratio of 1: 1 mol/mol; under the vibration of ultrasonic waves, adding the polyurea slurry obtained in the step 2) into the C component reinforced short fiber in the mold, so that the reinforced fiber or/and the cloth are completely soaked in the polyurea slurry, and pressing the mixture into a high-performance polyurea composite material under certain pressure; the composite material can be used for train body, house building and airplane interior decoration, and can also be used for internal corrosion prevention of large-scale chemical equipment.
Description
The technical field is as follows:
the invention relates to a method for manufacturing a high-performance polyurea composite material, and belongs to the field of high-performance composite materials.
Background art:
spray polyurea elastomer technology has undergone three stages of development, polyurethane, polyurethaneurea and polyurea. In the three systems, the component A is essentially identical, and is an aromatic or aliphatic prepolymer and a semi-prepolymer, with the difference being the component B. The component B of the spray polyurethane consists of hydroxyl-terminated resin and a hydroxyl-terminated chain extender, and contains a catalyst for improving the reaction activity.
The component B of the spray polyurethane/urea can be hydroxyl-terminated resin, or can be composed of amine-terminated resin and amine chain extender, and generally contains a catalyst for improving the reaction activity. The component B of the spray polyurea is required to be composed of an amino-terminated resin and an amino-terminated chain extender, does not contain any hydroxyl component and catalyst, and can contain a certain amount of a dispersing agent and neutral ash 2 BL.
Because the reaction activity of the amino-terminated compound and the isocyanate component is extremely high, the reaction can be instantly completed at room temperature or low temperature without any catalyst, thereby effectively overcoming the fatal defects that the polyurethane and polyurethane/urea elastomer are foamed due to the influence of environmental temperature and humidity in the construction process, and the material performance is rapidly reduced.
The polyurea spraying technology integrates the advantages of anticorrosive materials such as slurry, rubber, plastics and the like, and is one of the most advanced international anticorrosive technologies at present. The gel has the technical advantages that the gel is fast cured, can be sprayed on any curved surface without generating a flow phenomenon, the gel time is as short as 10s or less, and the walking strength can be achieved within 10 min; it is not sensitive to temperature and moisture, and is not influenced by ambient temperature and humidity during construction. The polyurea can be constructed in a low-temperature environment of-28 ℃ and can also be constructed in a humid and rainy environment; the paint has 100 percent of solid content, meets the requirement of environmental protection, has no smell in the construction and use processes, and is particularly suitable for the anticorrosion construction of the inner wall of a storage tank and the inner wall of a pipeline with poor ventilation; the requirement of thickness can be met by one-time construction, and the defect that the traditional anticorrosive slurry needs to be constructed for many times is overcome; the coating is compact and seamless, can resist the long-term corrosion of media such as water, seawater, acid, alkali, salt, oil and the like, and has outstanding resistance to chemical media and soil erosion; the mechanical strength is high, the elongation rate is good, the impact resistance is good, and the material is not easy to damage under the action of temperature alternation and external force impact; the adhesive force is good, the adhesive force is more than 10MPa on the steel which is sand blasted to Sa2.5 grade, and the steel does not fall off after long-term use; the breakdown voltage resistance is up to more than 20kv/mm, and the matching property with cathode protection is good; the catalyst is not contained, the ultraviolet light aging resistance is good, and the paint is not pulverized and cracked after being used outdoors for a long time; wide use temperature, can be used for a long time at the temperature of between 50 ℃ below zero and 121 ℃, and the modified high temperature resistant polyurea can be used for a long time below 150 ℃, and the like.
The polyurea spraying technology has excellent physical properties and construction performance, and is a novel coating technology. The material can completely or partially replace the traditional polyurethane, epoxy resin, glass fiber reinforced plastic, FBE and polyolefin compounds, and has wide application prospect in the industries of chemical corrosion prevention, pipelines, buildings, ships, water conservancy, traffic, machinery, mine wear resistance and the like.
The anticorrosive material for the metal chemical storage tank is generally divided into two categories, namely a lining and slurry. Commonly used liners include rubber liners, plastic liners, and glass fiber reinforced plastic liners. The rubber lining is made of natural rubber or synthetic rubber and can be used at normal temperature and pressure. The disadvantages are that the field heating vulcanization is needed, the construction process is very complicated, and the quality is difficult to ensure. The plastic lining is generally a prefabricated block material, a special pasting process is needed during construction, and leakage is easily caused at a joint, so that integral failure is caused. The glass fiber reinforced plastic lining adopts a manual pasting process, has large smell, pollutes the environment, needs a plurality of constructions and is difficult to ensure the construction quality.
The traditional anticorrosive slurry has the advantage of convenient construction, and can be used on the inner wall or the outer wall. However, these slurry systems generally have insufficient hardness and toughness, are highly susceptible to cracking under thermal stress or impact, premature cracking can result in leakage of stored fluids, and repair and maintenance costs are increased; the system contains organic solvent, which is harmful to human body and pollutes environment, and pinholes generated by solvent volatilization can cause penetration of corrosive medium; multiple construction is needed, the period is long, the efficiency is low, and the like.
The polyurea spraying technology effectively solves the problems, has obvious technical advantages when being applied to corrosion prevention engineering of the inner wall and the outer wall of a steel storage tank, and has been successfully applied to projects such as crude oil tanks, heavy oil tanks, sewage tanks, hydrochloric acid tank cars and the like of Daqing oil fields, Shengli oil fields, Xinjiang oil fields, Qilu petrochemical industries, Lanzhou petrochemical industries and Yueyang petrochemical industries.
In addition, the SPUA technology can also be used for chemical storage tanks with heat preservation requirements as a protective layer of a heat preservation layer. The traditional method is to wrap galvanized iron sheets outside polyurethane foam, but the existing joints are easy to cause water inflow, and the foam is quickly corroded and aged. And the adoption of the SPUA technology can play the dual roles of corrosion resistance and water resistance, has no seam, and is beautiful and practical.
In order to prevent chemical raw materials from leaking, storage tank cofferdams are built around some chemical storage tanks. Early storage tank cofferdams are simple and crude, are generally formed by enclosing concrete or concrete walls, and are paved with broken stones at the bottoms. Once a large amount of raw materials are leaked, the cofferdam can be temporarily stored, but a small amount of leaked chemical raw materials can permeate into soil to cause serious pollution to the soil. With the increasing importance of the developed countries on environmental protection, the storage tank cofferdam must be completely closed to protect the soil. The plastic lining is applied to the storage tank cofferdam and has the advantage of good corrosion resistance, but the construction process is complex, and particularly the construction is very difficult in places with complex shapes and many pipe fittings. In addition, the constructed plastic lining has a large number of seams and often causes leakage, however, the polyurea can resist the erosion of water and most chemical media and has the characteristics of no pollution, no flowing, quick construction and the like. More importantly, the polyurea elastomer after spraying has no seams, good flexibility and elongation rate of more than 300 percent, can connect the capillary cracks on the concrete substrate together, and has excellent anti-seepage effect. At present, the application of polyurea in northern western Tai and Alaska areas in foreign concrete storage tank cofferdams in large quantities indicates that polyurea can withstand severe weather tests. Besides the storage tank cofferdam, the similar application fields also include the protection of surfaces such as chemical engineering trenches, power plant drainage ditches, ground impermeable layers and the like.
Polyurea represents the current development of the international latest anticorrosion technology. Currently, many of the international well-known pipe works use polyurea or/and polyurethane foam in combination for oil and gas pipelines that need to be insulated.
With the popularization and development of the polyurea technology, the superiority of the polyurea technology is well known by people. In the near future, polyurea will become one of the main corrosion-resistant materials for the outer wall of pipes together with fusion bonded epoxy powder, 3 PE.
The SPUA material can also be widely used as the inner wall anticorrosion of nodular cast iron pipes, steel pipes and cement pipes. To achieve a service life of 50 years, the inner wall of a cast iron pipe or a steel pipe must be subjected to an anticorrosive treatment, and a cement mortar lining has been conventionally used. The cement mortar is the pipeline lining with the longest history, but is easy to crack after stress shrinkage, and has more surface defects (such as pitted surfaces, sand holes and hollows); the cement mortar lining causes the content of soluble substances to be improved, the hardness to be changed, and NH3Precipitation, leading to alkalization of the water; the instability of water also affects disadvantages of cement mortar and the like.
When CO is in water2The mortar is damaged and sand grains are lost when the over-balance concentration reaches 7mg/L, so that the water quality is influenced. The SPUA material used as an anticorrosive material for the inner wall of the cast iron pipe has the advantages of good adhesive force, no cracking, strong corrosion resistance and long service life; the surface is smooth, the hydraulic friction coefficient is less than that of a concrete pipe and a steel pipe, and the water delivery efficiency can be improved. Under the condition of the same pipe diameter, the power and the energy of the pump are saved by more than 20 percent, and the operating cost is greatly reduced; no scale formation, no pollution of water quality by bacteria microorganism in water, no secondary pollution, and no change of permanent water delivery and water quality cleanliness.
In chinese patent No: 201110101576.3 discloses a method for producing a water-soluble polyurea resin, wherein the polyurea resin obtained by the method is mainly used for coating an article. A part of polyurea resin permeates into the object, so that the adhesion between the polyurea resin and the object is improved, and the polyurea resin is mainly used for fiber coating, concrete coating, water prevention and the like. In the application process of the water-soluble polyurea, the application field is limited.
In chinese patent No: 201110403185.7, which satisfies the requirements of not requiring long-term curing, not being affected by environmental conditions when cured, and not becoming yellow upon exposure to air for a long period of time, but in fact, the curing time of the polyurea resin composition is relatively long.
In chinese patent No: 201210198415.5, the modified polyurea slurry is polyurea resin synthesized by A, B two components, and 20-50 nm zinc oxide or titanium dioxide is blended as inorganic modified filling material of polyurea resin, however, in the process of the invention, the granularity of the zinc oxide and titanium dioxide is increased.
Chinese patent application No: 201310132859.3 discloses a comprehensive spray polyurea slurry and its preparation method; in the patent, two-component raw materials are used for preparing the polyurea slurry, and because a certain amount of various additives are required to be properly added in the preparation process of the polyurea slurry, the proportions of various components in the raw materials of the B component are changed after the additives are added, so that obvious formula difference exists for A, B two-component polyurea slurry.
In view of the above technical shortcomings, the present invention provides a method for producing a high-performance, non-polluting polyurea composite material.
The invention content is as follows:
the invention aims to research a manufacturing process of a polyurea composite material, fully utilize the vibration of ultrasonic waves on the premise of not increasing the manufacturing cost, improve the performance characteristics of polyurea slurry by reasonably selecting process control conditions and raw materials, achieve the final aim of optimizing the performance and simultaneously reduce the industrial production cost of the polyurea slurry.
The patent researches and develops a manufacturing method of a solvent-free high-performance polyurea composite material, has better excellent waterproof, anticorrosion and antifouling performances, and is suitable for protection in various severe environments.
A manufacturing method of a high-performance polyurea composite material is a novel material with excellent mechanical performance and service performance, the mechanical performance is slightly weaker than that of spray polyurea, but the operation mode is simpler and more convenient, the application range is wider, the price is cheaper, and the high-performance polyurea composite material can be widely applied to the fields of corrosion prevention, water prevention, pollution prevention, wear resistance and the like of civil buildings and large-scale buildings and chemical equipment. Compared with the composite material on the market at present, the preparation method of the high-performance polyurea composite material has excellent mechanical performance, has no solvent pollution, can keep the mechanical performance stability for a long time, protects the environment to a certain extent, saves the cost, reduces the energy consumption, and can be applied to the field with more strict requirements on the environment and the performance.
The preparation process of high performance composite polyurea material features that the polyurea slurry consists of A, B, C component and A component of isocyanate; the component B consists of a liquid amine chain extender, polyaspartic acid ester, pigment, an anti-settling agent, a leveling agent and an auxiliary agent; the component C consists of reinforced fibers, and the mole number of each component is as follows:
the component A comprises: 1.0mol of isocyanate;
and B component: 0.1-0.3 mol of polyaspartic acid ester, 0.9-0.7 mol of liquid chain extender, 3-6 wt% of pigment and filler, 3-6 wt% of anti-settling agent and 3.0-6.0 wt% of flatting agent; 0.1-0.3 wt% of an auxiliary agent;
and C, component C: 10-40 wt% of reinforcing fibers are S-type glass short fibers, E-type glass short fibers and carbon short fibers;
firstly, mixing a B component liquid amine chain extender, polyaspartic acid ester, a pigment, an anti-settling agent, a leveling agent and an auxiliary agent in a mixing kettle to form a uniform solution, mixing the two components at a certain molar ratio of A, B, spraying the mixture on the surface of the C component, completely soaking the interior of the C component reinforced short fiber into A, B two component mixture under the condition of ultrasonic thin continuous vibration, immediately placing the C component reinforced short fiber soaked with A, B two component mixture in a mold for pressing for 30-120 min for forming, and removing the mold to finish the manufacturing of the high-performance polyurea composite material; the specific manufacturing process of the polyurea composite material is as follows:
1): adding polyaspartic acid ester and 3, 5' -diamino-p-chlorobenzoic acid isobutyl ester or/and 1, 3-propylene glycol-bis- (4-aminobenzoic acid) or/and bis (p-aminobenzoic acid) propylene glycol ester or/and bis (p-aminobenzoic acid) diethylene glycol ester liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 0.5-3.0 min at the stirring speed of 800-1000 rpm, adding 3-6 wt% of cardamon diethanolamide or cardamon monoethanolamide or oil diethanolamide or palm monoethanolamide anti-settling agent, stirring for 10-18 min at the stirring speed of 800-1000 rpm, sequentially adding 3-6 wt% of pigment and filler, 3.0-6.0 wt% of leveling agent, red BN color paste 01 or yellow color paste 30 or green color paste 51004 pigment in the formula of the component C, stirring for 4-8 min at a stirring speed of 600-900 rpm, adding a courtesy 431 or courtesy 432 leveling agent in the component C, stirring for 3.0-8.0 min at a stirring speed of 400-600 rpm, adding 0.1-0.3 wt% of BYK-80A or BYK-A500 or BYK-359 auxiliary agent, and stirring for 3.0-8.0 min at a stirring speed of 400-600 rpm to obtain a component B mixture D of the polyurea composite material.
2): mixing 2, 2, 4-trimethylhexane diisocyanate or/and dicyclohexyl methylene diisocyanate or/and isophorone diisocyanate or/and furan diisocyanate of the component A and 2) main components in a molar ratio of 1: 1mol/mol to form polyurea slurry for standby, wherein the main components comprise isocyanate, polyaspartic acid and a liquid chain extender in a molar ratio of 1: 1 mol/mol;
3) placing glass short fibers with the length of 1.0-12.0 mm and the fiber diameter of 3-12 umS types, E type glass short fibers and carbon short fiber reinforced fibers into a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in the step 2) into the reinforced short fibers under the vibration of the ultrasonic vibrator, and stopping ultrasonic vibration after the reinforced short fibers are completely soaked in the polyurea slurry, wherein the ultrasonic vibration frequency is 6.5x104～1.2x105Hz, and the vibration time is 33-58 s; covering the mold, applying 1.0-5.0 MPa pressure to the mold, pressing for 30-120 min for forming, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
the mechanical property of the high-performance polyurea composite material prepared by the method is tested by a JG/T235-2005 specified method, the tensile strength is more than 115.7MPa, the elongation at break is more than 150 percent, and the tearing strength is more than 181Nmm-1(ii) a The energy dissipation capacity characterization adopts the sample size and the stretching rate specified in JG/T235-2005, the hysteresis curve of the sample is tested, the energy dissipation efficiency is calculated and used for characterizing the dissipation capacity, and the test result shows that the high-performance polymer is high in performanceThe energy dissipation capacity of the manufacturing method of the urea composite material is obviously stronger than that of the common comprehensive slurry at present. The comprehensive temperature difference is tested by the method specified in JG/T235-2014, and the result shows that the comprehensive performance of the slurry is gradually increased along with the increase of the total mass fraction of the filler, and when the addition amount of the reinforcing short fibers reaches 26-28 wt%, the better comprehensive performance is obtained.
The functional pigment and filler are added into the resin system, so that certain properties of the slurry can be effectively and pertinently improved, and the slurry can be used in special environment, but the powder functional filler in the resin system usually affects the continuity of a macromolecular chain segment, and the mechanical properties of the material are reduced to a certain extent. In addition, the dispersion of the powder particles in the resin often requires dilution with a large amount of solvent, which not only increases the production cost, but also causes great pollution to the environment. The inventor adds the filler into the polyurea resin system, has excellent dispersibility without a solvent, and can keep better mechanical property. The invention is completed based on the process formula, and the filler and the secondary amine resin are physically blended to form the polyurea component D, and the polyurea component D and the polyurea component A react at normal temperature to be cured into a film, and the film is dried to prepare the molded high-performance polyurea composite material.
In order to further improve the impact strength of the polyurea resin, in the process of the invention, the invention adopts a full-polyurea resin formula, and aims to improve the strength of the polyurea slurry.
The preparation method of the high-performance polyurea composite material provided by the invention has excellent mechanical properties and operating properties, does not need to add extra solvent in the production process, is completely cured in use, does not discharge organic micromolecular harmful substances, and is novel environment-friendly slurry. The heat reflection pigment and filler are added into the polyurea system in a physical blending mode, and the heat reflection pigment and filler reflect most of sunlight reaching the surface of the coating, so that the absorption of the wall surface on solar energy is prevented, the temperature inside and on the surface of a building is effectively reduced, the production process is simple and easy to operate, and the comprehensive performance of the polyurea resin can be directly and effectively improved; meanwhile, the manufacturing method system of the high-performance polyurea composite material can show excellent mechanical performance, and can resist the phenomena of coating cracking, fault, peeling and the like caused by the change of external environment in the using process to a certain extent. The method not only avoids the use of organic solvent, saves the production cost, but also does not damage the environment, more importantly solves the problem that most of the existing comprehensive slurry has extremely poor mechanical properties, prolongs the service life of the slurry and widens the application field of the comprehensive slurry. The preparation method of the high-performance polyurea composite material provided by the invention has the advantages of high strength, excellent comprehensive performance, low production cost, simple manufacturing process, no environmental pollution and easy realization of large-scale industrial production.
In the process of the invention, the purpose of adding the leveling agent properly is to facilitate the construction of the polyurea slurry, which is beneficial to the flow of the slurry, no matter manual or spraying, and certainly if the addition amount of the leveling agent is too much, the polyurea slurry is easy to generate a pearl hanging phenomenon in the construction process of the polyurea slurry in the building, which affects the construction quality on one hand, and on the other hand, the polyurea slurry is too wasted.
In the process of the present invention, the purpose of the proper addition of the auxiliary agent is to eliminate the air bubbles entrained by the polyurea slurry components during the stirring process, so as to reduce the air bubble content in the polyurea coating and simultaneously improve the compactness of the polyurea slurry.
The invention adopts ultrasonic vibration to properly improve the distribution of the reinforcing fiber in the polyurea resin, and as the reinforcing short fiber and the component B raw material are not mixed together, the invention finds out through repeated experiments that the control of the time frequency of the ultrasonic vibration is very important in order to improve the uniform distribution degree of the reinforcing short fiber in the polyurea resin, and when the ultrasonic vibration frequency is controlled at 6.5x104～1.2x105Hz, the vibration time is within the range of 33-58 s, the uniform distribution degree of the reinforced short fibers in the polyurea resin can be improved by 15-30%, the distribution degree of the reinforced short fibers in the polyurea resin directly influences the comprehensive performance of the polyurea composite material, when the distribution is not uniform, the positions with more polyurea resin and less elongation at break are increased by nearly 5 times, after the reinforced short fibers are relatively uniform, the elongation at break basically changes between 4-6%, no influence is caused on the comprehensive performance of the polyurea composite material, and meanwhile, when the frequency of ultrasonic waves is too high and the vibration time is shorter than the time of the invention, the phenomenon that the reinforced short fibers in the polyurea resin are agglomerated is found, so that the comprehensive performance of the polyurea composite material is reduced; when the vibration frequency of the ultrasonic wave is low and the vibration time is longer than the time of the present invention, it is also found that the reinforcing short fibers in the polyurea resin are agglomerated, so that the overall properties of the polyurea composite material are lowered.
The mold used in the process of the present invention may be selected in any shape as required, or may be selected according to the main body to be decorated, wherein the main shape is a cylindrical shape, a rectangular parallelepiped shape, or a conical shape, and if the main body is an arc shape, the mold is also the arc shape.
Drawings
FIG. 1 shows the performance characteristics of the high-performance polyurea composite material of the invention
The process flow introduction of the invention is as follows:
a method for preparing high-performance polyurea composite material, firstly mixing component B of liquid amine chain extender, polyaspartic acid ester and anti-settling agent in a mixing kettle to form uniform solution, and then adding pigment, flatting agent and auxiliary agent; under the condition of a certain stirring speed, the mixture becomes a mixture of the component D; mixing the main components of the mixture of the component A and the component D in a ratio of 1: 1mol/mol to form polyurea slurry, placing reinforced short fibers in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in the step 2) into the reinforced short fibers under the vibration of the ultrasonic vibrator, stopping the ultrasonic vibration after the reinforced fibers or/and cloth are completely soaked in the polyurea slurry, covering the mold, applying a certain pressure to the mold, pressing for a certain time, and removing the mold to finish the manufacture of the high-performance polyurea composite material.
Detailed Description
The present invention will now be described specifically by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
Example 1:
1): adding 0.1mol of polyaspartic acid ester and 0.9mol of 3, 5' -diamino-p-chlorobenzoic acid isobutyl ester liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 3.0min at the stirring speed of 800rpm, adding 3 wt% of cardamodiethanolamide anti-settling agent, stirring for 18min at the stirring speed of 800rpm, sequentially adding 3 wt% of red slurry BN01 pigment in the formula of the component C, stirring for 8min at the stirring speed of 600rpm, adding 3.0 wt% of Delhi 431 flatting agent in the component C, stirring for 8.0min at the stirring speed of 400rpm, adding 0.1 wt% of BYK-80A auxiliary agent, and stirring for 8.0min at the stirring speed of 400rpm to obtain a component B mixture D of the polyurea composite material.
2): mixing 1.0mol of 2, 2, 4-trimethylhexane diisocyanate of the component A and 2) main components in a molar ratio of 1: 1mol/mol to form polyurea slurry for later use, wherein the main components comprise isocyanate, polyaspartic acid and a liquid chain extender in a molar ratio of 1: 1 mol/mol;
3) placing 10 wt% of glass short fiber having a length of 1.0mm and a fiber diameter of 3umS type in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in 2) to the reinforcing short fiber under the vibration of the ultrasonic vibrator, and stopping the ultrasonic vibration after the reinforcing short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 6.5x104Hz, the vibration time is 58 s; covering the mold, applying 0.1MPa pressure to the mold, pressing for 120min, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Example 2:
1): adding 0.3mol of polyaspartic acid ester and 0.7mol of 3, 5' -diamino-p-chlorobenzoic acid isobutyl ester liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 0.5min at the stirring speed of 1000rpm, adding 6 wt% of myristyl diethanolamide anti-settling agent, stirring for 10min at the stirring speed of 1000rpm, sequentially adding 6 wt% of red slurry BN01 pigment in the formula of the component C, stirring for 4min at the stirring speed of 900rpm, adding 6.0 wt% of Delhi 431 flatting agent in the component C, stirring for 3.0min at the stirring speed of 600rpm, adding 0.3 wt% of BYK-80A auxiliary agent, and stirring for 3.0min at the stirring speed of 600rpm to obtain a component B mixture D of the polyurea composite material.
2): mixing 1.0mol of 2, 2, 4-trimethylhexane diisocyanate of the component A and 2) main components in a molar ratio of 1: 1mol/mol to form polyurea slurry for later use, wherein the main components comprise isocyanate, polyaspartic acid and a liquid chain extender in a molar ratio of 1: 1 mol/mol;
3) placing 40 wt% of glass short fiber having a length of 12.0mm and a fiber diameter of 12umS type in a mold equipped with an ultrasonic vibrator, adding 2) the obtained polyurea slurry to the reinforcing short fiber under the vibration of the ultrasonic vibrator, and stopping the ultrasonic vibration after the reinforcing short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 1.2x105Hz, the vibration time is 33 s; covering the mold, applying 0.3MPa pressure to the mold, pressing for 30min, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Example 3:
1): adding 0.2mol of polyaspartic acid ester and 0.8mol of 1, 3-propylene glycol-bis- (4-aminobenzoic acid) liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 1.8min at the stirring speed of 850rpm, adding 3.5 wt% of cardamon monoethanolamide anti-settling agent, stirring for 15min at the stirring speed of 900rpm, sequentially adding 4 wt% of yellow slurry 51030 and pigment in the formula of the component C, stirring for 6min at the stirring speed of 700rpm, adding 5.0 wt% of Demoden 431 leveling agent in the component C, stirring for 6.0min at the stirring speed of 500rpm, adding 0.3 wt% of BYK-A500 auxiliary agent, and stirring for 7.0min at the stirring speed of 500rpm to obtain a component B mixture D of the polyurea composite material.
2): 1.0mol of dicyclohexyl methylene diisocyanate of the A component and 2) main components are mixed into polyurea slurry for standby according to the mol ratio of 1: 1mol/mol, wherein the main components are isocyanate, polyaspartic acid and liquid chain extender, and the mol ratio of the isocyanate to the polyaspartic acid to the liquid chain extender is 1: 1 mol/mol;
3) placing 16 wt% of glass short fiber having a length of 4.0mm and a fiber diameter of 6umE type in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in 2) to the reinforcing short fiber under the vibration of the ultrasonic vibrator, and stopping the ultrasonic vibration after the reinforcing short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 7.3x104Hz, vibration time is 51 s; covering the mold, applying 0.1MPa pressure to the mold, pressing for 68min for forming, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Comparative example 1:
1): adding 0.1mol of polyaspartic acid ester and 0.9mol of 3, 5' -diamino-p-chlorobenzoic acid isobutyl ester liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 3.0min at the stirring speed of 800rpm, adding 3 wt% of cardamodiethanolamide anti-settling agent, stirring for 18min at the stirring speed of 800rpm, sequentially adding 3 wt% of red slurry BN01 and pigment in the formula of the component C, stirring for 8min at the stirring speed of 600rpm, adding 3.0 wt% of Delhi 431 leveling agent in the component C, stirring for 8.0min at the stirring speed of 400rpm, adding 0.1 wt% of BYK-80A auxiliary agent, and stirring for 8.0min at the stirring speed of 400rpm to obtain a component B mixture D of the polyurea composite material.
2): mixing 1.0mol of 2, 2, 4-trimethylhexane diisocyanate of the component A and 2) main components in a molar ratio of 1: 1mol/mol to form polyurea slurry for later use, wherein the main components comprise isocyanate, polyaspartic acid and a liquid chain extender in a molar ratio of 1: 1 mol/mol;
3) placing 10 wt% of glass short fiber having a length of 1.0mm and a fiber diameter of 3umS type in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in 2) to the reinforcing short fiber under the vibration of the ultrasonic vibrator, and stopping the ultrasonic vibration after the reinforcing short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 3.5x104Hz, the vibration time is 88 s; covering the mold, applying 0.1MPa pressure to the mold, pressing for 120min, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Example 4:
1): adding 0.15mol of polyaspartic acid ester and 0.85mol of bis (p-aminobenzoic acid) propylene glycol ester liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 2.0min at the stirring speed of 960rpm, adding 5 wt% of oil diethanolamide anti-settling agent, stirring for 10min at the stirring speed of 800rpm, sequentially adding 5 wt% of green slurry 51004 pigment in the formula of the component C, stirring for 8min at the stirring speed of 900rpm, adding 5.0 wt% of Delhi 431 leveling agent in the component C, stirring for 8.0min at the stirring speed of 600rpm, adding 0.2 wt% of BYK-359 additive, and stirring for 8.0min at the stirring speed of 600rpm to obtain a component B mixture D of the polyurea composite material.
2): mixing 1.0mol of isophorone diisocyanate of the component A and 2) main components in a ratio of 1: 1mol/mol into polyurea slurry for standby application, wherein the main components are isocyanate, polyaspartic acid and a liquid chain extender in a molar ratio of 1: 1 mol/mol;
3) placing 26% of carbon short fiber with length of 10.0mm and fiber diameter of 8umS type in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in step 2) to the reinforced short fiber under the vibration of the ultrasonic vibrator, and stopping ultrasonic vibration after the reinforced short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 1.1x105Hz, the vibration time is 58 s; covering the mold, applying 0.3MPa pressure to the mold, pressing for 71min for forming, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Example 5:
1): adding 0.25mol of polyaspartic acid ester and 0.75mol of bis (p-aminobenzoic acid) diethylene glycol ester liquid amine chain extender in the formula of the component B into a mixing kettle, stirring for 3.0min at the stirring speed of 1000rpm, adding 3 wt% of palmityl monoethanolamide anti-settling agent, stirring for 10min at the stirring speed of 800rpm, sequentially adding 3 wt% of green slurry 51004 pigment in the formula of the component C, stirring for 4-8 min at the stirring speed of 600-900 rpm, adding 3.0 wt% of Delhi 432 flatting agent in the component C, stirring for 3.0min at the stirring speed of 400rpm, adding 0.1 wt% of BYK-359 additive, and stirring for 3.0min at the stirring speed of 400rpm to obtain a component B mixture D of the polyurea composite material.
2): 1.0mol of furan diisocyanate of the component A and 2) main components are mixed into polyurea slurry according to the mol ratio of 1: 1mol/mol for standby application, wherein the main components are isocyanate, polyaspartic acid and liquid chain extender, and the mol ratio of the isocyanate to the polyaspartic acid to the liquid chain extender is 1: 1 mol/mol;
3) placing 28 wt% of glass short fiber with length of 12.0mm and fiber diameter of 12umS type, E type glass short fiber and carbon short fiber reinforced fiber in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in step 2) into the reinforced short fiber under the vibration of the ultrasonic vibrator, and stopping ultrasonic vibration after the reinforced short fiber is completely soaked in the polyurea slurry, wherein the ultrasonic vibration frequency is 9.5x104Hz, the vibration time is 33 s; covering the mold, applying 0.25MPa pressure to the mold, pressing for 120min to form, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Example 6:
1): adding 0.3mol of polyaspartic acid ester and 0.7mol of 1, 3-propanediol-bis- (4-aminobenzoic acid) and bis (p-aminobenzoic acid) propanediol liquid amine chain extender in the formula of the component B into a mixing kettle, wherein the molar ratio of 1, 3-propanediol-bis- (4-aminobenzoic acid) to bis (p-aminobenzoic acid) propanediol ester is 1: 3; stirring for 1.5min at the stirring speed of 900rpm, adding 4 wt% of oil diethanolamide anti-settling agent, stirring for 14min at the stirring speed of 900rpm, sequentially adding 5 wt% of yellow slurry 51030 pigment in the formula of the component C, stirring for 6min at the stirring speed of 700rpm, adding 4 wt% of Delhi 431 leveling agent in the component C, stirring for 6.0min at the stirring speed of 500rpm, adding 0.2 wt% of BYK-A500 auxiliary agent, and stirring for 7.0min at the stirring speed of 500rpm to obtain a component B mixture D of the polyurea composite material.
2): mixing 1.0mol of 2, 2, 4-trimethylhexane diisocyanate and dicyclohexyl methylene diisocyanate of the component A and 2) of main components into polyurea slurry for standby at a molar ratio of 1: 1mol/mol, wherein the main components are isocyanate, polyaspartic acid and liquid chain extender at a molar ratio of 1: 1 mol/mol; wherein the molar ratio of the 2, 2, 4-trimethylhexane diisocyanate to the dicyclohexylmethylene diisocyanate is 3: 1.
3) Placing 35 wt% of glass short fiber having a length of 6mm and a fiber diameter of 4umE type in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in 2) to the reinforcing short fiber under the vibration of the ultrasonic vibrator, and stopping the ultrasonic vibration after the reinforcing short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 8.5x104Hz, the vibration time is 44 s; covering the mold, applying 0.1MPa pressure to the mold, and pressing for 80min to obtainAfter forming, removing the mould to finish the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
Comparative example 2:
1): adding 0.3mol of polyaspartic acid ester and 0.7mol of 3, 5' -diamino-p-chlorobenzoic acid isobutyl ester liquid amine chain extender in the B component formula into a mixing kettle, stirring for 0.5min at the stirring speed of 1000rpm, then adding 6 wt% of cardamodiethanolamide, or cardamonolamide, or oil diethanolamide, or palm monoethanolacyl anti-settling agent, stirring for 10min at the stirring speed of 1000rpm, sequentially adding 6 wt% of red slurry BN01 pigment in the C component formula, stirring for 4min at the stirring speed of 900rpm, then adding 6.0 wt% of DeBY431 and a leveling agent in the C component, stirring for 3.0min at the stirring speed of 600rpm, then adding 0.3 wt% of K-80A and an auxiliary agent, and stirring for 3.0min at the stirring speed of 600rpm to obtain a B component mixture D of the polyurea composite material.
2): mixing 1.0mol of 2, 2, 4-trimethylhexane diisocyanate of the component A and 2) main components in a molar ratio of 1: 1mol/mol to form polyurea slurry for later use, wherein the main components comprise isocyanate, polyaspartic acid and a liquid chain extender in a molar ratio of 1: 1 mol/mol;
3) placing 40 wt% of glass short fiber having a length of 12.0mm and a fiber diameter of 3umS type in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in 2) to the reinforcing short fiber under the vibration of the ultrasonic vibrator, and stopping the ultrasonic vibration after the reinforcing short fiber is completely impregnated with the polyurea slurry, wherein the ultrasonic vibration frequency is 1.8x105Hz, the vibration time is 33 s; covering the mold, applying 0.3MPa pressure to the mold, pressing for 30min, and removing the mold to complete the manufacture of the high-performance polyurea composite material;
a, D components are mixed according to the proportion of 1: 1.3 and coated on the surface of glass, and the polyurea comprehensive coating film is obtained after drying in an oven at 50 ℃. The properties of the sheets obtained are given in Table 1
As can be seen from the data of examples 1-6 and comparative examples 1-2, the manufacturing method of the high-performance polyurea composite material manufactured by the invention has stronger comprehensive performance, and the strength and the energy dissipation capability of the high-performance polyurea composite material are far stronger than those of common acrylate, polyurethane and epoxy comprehensive slurry at present.
Claims (7)
1. The preparation process of high performance composite polyurea material features that the polyurea slurry consists of A, B, C component and A component of isocyanate; the component B consists of a liquid amine chain extender, polyaspartic acid ester, pigment, an anti-settling agent, a leveling agent and an auxiliary agent; the component C consists of reinforced fibers, and the mole number of each component is as follows:
the component A comprises: 1.0mol of isocyanate;
and B component: 0.1-0.3 mol of polyaspartic acid ester, 0.9-0.7 mol of liquid chain extender, 3-6 wt% of pigment and filler, 3-6 wt% of anti-settling agent and 3.0-6.0 wt% of flatting agent; 0.1-0.3 wt% of an auxiliary agent;
and C, component C: 10 to 40 wt% of reinforcing fibers.
2. The method for preparing a high-performance polyurea composite material according to claim 1, wherein the method for preparing the polyurea composite material comprises the steps of mixing the component B, namely the liquid amine chain extender, the polyaspartic acid ester, the pigment, the anti-settling agent, the leveling agent and the auxiliary agent into a uniform solution in a mixing kettle, mixing the two components at a certain molar ratio of A, B, spraying the mixture on the surface of the component C, completely soaking the interior of the component C reinforcing short fiber into the mixture of the two components A, B under the condition of ultrasonic thin and continuous vibration, immediately placing the component C reinforcing short fiber soaked with the mixture of the two components A, B in a mold, pressing for 30-120 min for forming, and removing the mold to complete the preparation of the high-performance polyurea composite material; the specific manufacturing process of the polyurea composite material is as follows:
1) adding polyaspartic acid ester and a liquid amine chain extender in a B component formula into a mixing kettle, stirring for 0.5-3.0 min at a stirring speed of 800-1000 rpm, adding 3-6 wt% of an anti-settling agent, stirring for 10-18 min at a stirring speed of 800-1000 rpm, sequentially adding 3-6 wt% of pigment and filler and 3.0-6.0 wt% of a leveling agent in the C component formula, adding a pigment, stirring for 4-8 min at a stirring speed of 600-900 rpm, adding the leveling agent in the C component, stirring for 3.0-8.0 min at a stirring speed of 400-600 rpm, adding 0.1-0.3 wt% of an auxiliary agent, and stirring for 3.0-8.0 min at a stirring speed of 400-600 rpm to obtain a B component mixture of the polyurea composite material.
2) Mixing the component A and 2) main components in a ratio of 1: 1mol/mol to obtain polyurea slurry for standby, wherein the main components are isocyanate: the molar ratio of the polyaspartic acid to the liquid chain extender is 1: 1 mol/mol;
3) placing the reinforced short fibers in a mold equipped with an ultrasonic vibrator, adding the polyurea slurry obtained in the step 2) into the reinforced short fibers under the vibration of the ultrasonic vibrator, and stopping ultrasonic vibration after the reinforced short fibers are completely soaked in the polyurea slurry, wherein the ultrasonic vibration frequency is 6.5x104～1.2x105Hz, and the vibration time is 33-58 s; covering the mold, applying a pressure of 0.1-0.3 MPa to the mold, pressing for 30-120 min, and removing the mold to complete the manufacture of the high-performance polyurea composite material.
3. The method of claim 1, wherein the isocyanate is 2, 2, 4-trimethylhexane diisocyanate, dicyclohexylmethylene diisocyanate, isophorone diisocyanate, or furan diisocyanate.
4. The method of claim 1, wherein the amine chain extender is selected from isobutyl 3, 5' -diamino-p-chlorobenzoate, 1, 3-propanediol-bis- (4-aminobenzoic acid), propylene glycol bis (p-aminobenzoate), diethylene glycol bis (p-aminobenzoate).
5. The method for preparing a high-performance flame-retardant polyurea paste according to claim 1, wherein the pigment is red paste BN01, yellow paste 51030 and green paste 51004.
6. The method for preparing the high-performance flame-retardant polyurea slurry according to claim 1, wherein the auxiliary agent comprises an anti-settling agent, an auxiliary agent, a leveling agent and the like; wherein the anti-settling agent is selected from the group consisting of cardamon diethanolamide, cardamon monoethanolamide, oleyl diethanolamide, and palmityl monoethanolamide; the auxiliary agents are BYK-80A, BYK-A500 and BYK-359; leveling agents are modesty 431 and modesty 432.
7. The method of claim 1, wherein the reinforcement fibers are S-type glass staple fibers, E-type glass staple fibers, carbon staple fibers; wherein the length of the short fiber is 1.0-12.0 mm, and the fiber diameter is 3-12 um.
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