CN114573951A - Rapid curing epoxy resin system for glass fiber pultrusion frame and preparation method thereof - Google Patents
Rapid curing epoxy resin system for glass fiber pultrusion frame and preparation method thereof Download PDFInfo
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- CN114573951A CN114573951A CN202210350843.9A CN202210350843A CN114573951A CN 114573951 A CN114573951 A CN 114573951A CN 202210350843 A CN202210350843 A CN 202210350843A CN 114573951 A CN114573951 A CN 114573951A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/08—Epoxidised polymerised polyenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1856—Stationary reactors having moving elements inside placed in parallel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a rapid curing epoxy resin system for a glass fiber pultrusion frame and a preparation method thereof, belonging to the field of glass fiber processing. The invention relates to a rapid curing epoxy resin system for a glass fiber pultrusion frame and a preparation method thereof, wherein the rapid curing epoxy resin system comprises the following components in parts by weight: 50-75 parts of polybutadiene epoxy resin, 50-75 parts of glycidyl ether type epoxy resin, 15-30 parts of modified toughening particles, 8-12 parts of curing agent, 30-40 parts of liquid crystal epoxy resin, 25-30 parts of B144 epoxy resin, 10-20 parts of inorganic whiskers, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion. The invention effectively improves the wear-resisting effect of the epoxy resin system by adding the high polymer waterproof emulsion and the dendritic polymer, is convenient to be connected with a machine, carries out the work of preparing the glass fiber and effectively improves the working quality.
Description
Technical Field
The invention relates to the technical field of glass fiber processing, in particular to a rapid curing epoxy resin system for a glass fiber pultrusion frame and a preparation method thereof.
Background
The glass fiber is an inorganic non-metallic material with excellent performance, has various varieties, has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the defects of brittleness and poor wear resistance. The fiber is made by using glass balls or waste glass as raw materials and carrying out processes of high-temperature melting, wire drawing, winding, weaving and the like, wherein the diameter of each monofilament ranges from several micrometers to twenty micrometers, and each fiber strand consists of hundreds of monofilaments and even thousands of monofilaments. Glass fibers are commonly used as reinforcing materials in composite materials, electrical and thermal insulation materials, circuit substrates, and other various fields of the national economy.
The pultrusion of glass fibers requires a mold for processing, and is generally performed using an epoxy resin frame.
The existing epoxy resin molding frame has the following defects in the using process:
1. the strength is poor, and the long-term work cannot be adapted.
2. The wear-resisting effect is general, and in the cooperation work with mechanical equipment, easily produce wearing and tearing, influence processingquality.
In view of these drawbacks, it is desirable to design a fast curing epoxy resin system for glass fiber pultrusion frames and a method for making the same.
Disclosure of Invention
The invention aims to provide a fast curing epoxy resin system for a glass fiber pultrusion frame and a preparation method thereof, which can solve the problems that in the prior art, an epoxy resin molding frame is poor in strength, general in wear-resisting effect, easy to wear and affect processing quality when being matched with mechanical equipment.
In order to achieve the purpose, the invention provides the following technical scheme: the fast curing epoxy resin system for the glass fiber pultrusion frame comprises the following components in parts by weight: 50-75 parts of polybutadiene epoxy resin, 50-75 parts of glycidyl ether type epoxy resin, 15-30 parts of modified toughening particles, 8-12 parts of a curing agent, 30-40 parts of liquid crystal epoxy resin, 25-30 parts of B144 epoxy resin, 10-20 parts of inorganic whiskers, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion, wherein the dendritic polymer comprises aromatic diisocyanate and G0 dendritic PAMAM, and the high polymer waterproof emulsion comprises wear-resistant ceramic particle glue, emulsion and inorganic powder.
Preferably, the polybutadiene epoxy resin is a high-molecular polymer formed by mixing epoxidized polybutadiene resin, E-51 epoxy resin, isocyanate, low-molecular polyamide and a modified amine curing agent, and the glycidyl ether type epoxy resin is a glycidyl ether type polymer formed by condensation polymerization of ethylene glycol, glycerol, pentaerythritol, polyglycidyl glycol and epichlorohydrin.
Preferably, the modified toughening particles comprise rubber elastomers, core-shell polymers, thermoplastic resins, thermotropic liquid crystal polymers and nanoparticles, wherein the rubber elastomers comprise amino-terminated butadiene-acrylonitrile rubber and carboxyl-terminated butadiene-acrylonitrile rubber.
Preferably, the liquid crystal epoxy resin is obtained by introducing a monomer having a liquid crystal behavior in a reaction during the synthesis of the epoxy resin, curing the epoxy compound within a temperature range of the liquid crystal phase monomer, and performing isotropic-to-liquid crystal transition during the curing of the system, so that the ordered arrangement of the liquid crystal molecules is finally fixed by intermolecular crosslinking.
Preferably, the inorganic whiskers include zinc oxide whiskers, calcium sulfate whiskers, calcium carbonate whiskers and silicon carbide whiskers, and the preparation method of the inorganic whiskers includes the following steps:
the method comprises the following steps: simultaneously adding zinc oxide powder, calcium sulfate powder, calcium carbonate powder and silicon carbide powder into inorganic acid and stirring;
step two: introducing the sodium silicate solution into the inorganic acid mixed solution according to the ratio;
step three: adjusting the pH value of the mixed solution to 8-9;
step four: filtering the solution, and drying to obtain the inorganic crystal whisker.
The preparation method of the rapid curing epoxy resin system for the glass fiber pultrusion frame comprises the following steps:
s1: the polybutadiene epoxy resin is proportionally weighed, namely epoxy polybutadiene resin, 95-70% of E-51 epoxy resin, isocyanate, low molecular polyamide and modified amine curing agent are introduced into a first reaction kettle to be mixed, and then high molecular polymer is prepared after mixing;
s2: mixing ethylene glycol, glycerol, pentaerythritol and polyglycidyl, introducing the mixture into a second reaction kettle, heating the mixture by a heater, introducing epoxy chloropropane into the second reaction kettle during heating, and concentrating the epoxy chloropropane to obtain glycidyl ether type epoxy resin;
s3: adding a high molecular polymer, glycidyl ether type epoxy resin, 25-30 parts of B144 epoxy resin, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion into a third reaction kettle, heating to 140 ℃ under the protection of inert atmosphere, and carrying out heat preservation stirring reaction for 35-40 min;
s4: after the reaction, adding 15-30 parts of modified toughening particles, 10-20 parts of inorganic whiskers and 15-20 parts of dendritic polymers into a third reaction kettle, adjusting the temperature to 170-180 ℃, and continuously stirring for 3-8 hours;
s5: after stirring, adding 20-25 parts of high polymer waterproof emulsion and 8-12 parts of curing agent, adjusting the temperature to 120-130 ℃, stirring for 15-20 min, and then performing rotary evaporation to remove organic matters to obtain epoxy resin;
s6: and (3) passing the epoxy resin through a forming frame die to prepare a glass fiber pultrusion forming frame die with corresponding specification.
Preferably, first reation kettle in S1 includes the guide fill, the guide fill is provided with threely, and is three the lower extreme of guide fill all is provided with the unloading valve of weighing, just sealed apron is installed to first reation kettle ' S upper end, speed reducer and servo motor are installed to the upper end of sealed apron, first reation kettle ' S internally mounted has first stirring rake, the connecting axle is installed to the upper end of first stirring rake, speed reducer and servo motor transmission are connected, just the speed reducer passes through the connecting axle and is connected with first stirring rake transmission, first reation kettle ' S externally mounted has the guard ring.
Preferably, the number of the heaters in S2 is two, the two heaters are respectively located on two sides of the lower end inside the second reaction kettle, the lower ends of the second reaction kettle and the first reaction kettle are both provided with a feeding pipe, and the lower end of the feeding pipe is provided with a material guide pipe.
Preferably, the access panel is installed to the upper end of the third reation kettle in S3, the motor is installed to the upper end of access panel, the second stirring rake is installed to the lower extreme of motor, the motor is connected with the transmission of second stirring rake, just the conveying pipe is installed to the lower extreme of third reation kettle, two the guide pipe all extends to the inside and third reation kettle sealing connection of third reation kettle, the inside upper end of third reation kettle is provided with the feed inlet, the conveying pipe is installed to the below of third reation kettle front end.
Preferably, become frame mould among S6 includes the one-tenth die cavity and stereotypes the board, become the die cavity setting around the board of finalizing the design, the upper end of finalizing the design board is provided with the material receiving mouth, the inside of material receiving mouth is provided with the board of finalizing the design, just the inside of finalizing the design board is provided with the water conservancy diversion passageway, the internally mounted of water conservancy diversion passageway has the solenoid valve, the position of conveying pipe is corresponding with the position of material receiving mouth.
Compared with the prior art, the invention has the following beneficial effects:
1. the existing glass fiber pultrusion forming frame needs to be continuously contacted with glass fiber for shaping in long-term work, needs to be continuously moved, adjusts the position for loading and unloading work in the work process, and has unstable structure to cause gradual reduction of the work quality in long-term work, in the invention, the wear-resisting effect of an epoxy resin system is efficiently improved by adding high polymer waterproof emulsion and dendritic polymer, thereby being convenient for long-term mechanical connection for preparing the glass fiber, effectively improving the work quality, improving the adhesive property of raw materials of the epoxy resin system by the high polymer waterproof emulsion, and improving the durability of inorganic materials, and the high polymer waterproof emulsion has the advantages of high compressive strength, rapid curing and good adhesive property, and has good water retention property and crack resistance, high alkali resistance, ultraviolet resistance and the like, and is uniformly coated on the outer surface of the epoxy resin system, the wear-resistant ceramic particle glue in the high polymer waterproof emulsion has excellent toughness and shock resistance, and the toughness is further improved by coupling due to the adoption of a directional net reinforcing measure, so that the wear-resistant ceramic particle glue is high in fracture resistance and toughness, and can effectively prevent damage and peeling caused by impact force.
2. The rapid curing epoxy resin system for the glass fiber pultrusion molding frame and the preparation method thereof, the G0 dendritic PAMAM forms a shell packaging structure with self-repairing performance and good strength performance on the surface of the epoxy resin system through the interaction of a cross-linking structure and a better interface of chemical bonding with a polymer adhesive, the durability of the epoxy resin is effectively improved, the optimal working strength is achieved, the shaping work is carried out by matching with machinery, the adaptability is good, the stability is high, the polybutadiene epoxy resin has excellent electrical insulation performance, good thermal stability and chemical stability, the resistivity and the dielectric property of the EP resin can be obviously improved, active groups contained in isocyanate can effectively connect EP and hydroxyl-terminated polybutadiene, the compatibility between two phases is increased, the impact strength of modified EP is greatly improved, and the glycidyl ether type epoxy resin not only retains the ultraviolet radiation resistant performance of the traditional alicyclic epoxy resin, The cured product has good comprehensive mechanical and electrical properties, has a long service life after being mixed with the curing agent, can be widely applied to glass fiber forming work, has a wide application range and a stable structure, and the carboxyl-terminated butadiene-acrylonitrile rubber has nitrile groups with high polarity and good molecular flexibility, a sea-island state phase separation microstructure which is beneficial to improving the toughness of the composite material is formed in a toughening EP system, different material components are respectively enriched inside and outside the core-shell polymer, so that the functions of the core and the shell are different, and the core-shell polymer has good flocculation property and is incompatible with EP after being blended, a complete sea-island state phase separation structure can be formed after curing, and the toughness of EP can be obviously improved by controlling the components and the particle size of the core-shell polymer, therefore, after the glass fiber pultrusion frame is processed, the strength can be kept for a long time, and after the glass fiber pultrusion frame is contacted with the glass fiber, the glass fiber pultrusion frame has certain elasticity and keeps the stability of the frame body.
3. The fast curing epoxy resin system for glass fiber drawing and extruding frame and its preparation process includes the steps of compounding liquid crystal epoxy resin and thermoplastic resin, toughening with less amount of liquid crystal epoxy resin, forming homogeneous liquid crystal area between isotropic liquid and completely ordered crystal, forming heterogeneous liquid crystal epoxy resin, forming homogeneous silver grain in the homogeneous disordered area and propagating along the external force direction, and blocking the silver grain in the homogeneous liquid crystal area to raise the breaking strength of the liquid crystal epoxy resin greatly, therefore, the high-performance resin material for the glass fiber forming frame has the advantages of high temperature resistance, high strength, high wave permeability, wave absorption and the like, so that the resin matrix composite material toughened by the silicon carbide whiskers can effectively meet the requirements.
Drawings
FIG. 1 is an overall front view of a production apparatus of the present invention;
FIG. 2 is an overall front view from another angle of the manufacturing apparatus of the present invention;
FIG. 3 is an internal structural view of the forming frame mold of the present invention;
FIG. 4 is a view showing the internal structure of a first reaction vessel, a second reaction vessel and a third reaction vessel of the present invention.
In the figure: 1. a first reaction kettle; 101. a material guide hopper; 102. a speed reducer; 103. a servo motor; 104. a weighing blanking valve; 105. sealing the cover plate; 106. a guard ring; 107. a feeding pipe; 108. a material guide pipe; 109. a first stirring paddle; 110. a connecting shaft; 2. a second reaction kettle; 201. a heater; 3. a third reaction kettle; 301. an electric motor; 302. an access panel; 303. a feed pipe; 304. a second stirring paddle; 305. a feed inlet; 4. forming a frame mold; 401. a molding cavity; 402. a material receiving port; 403. shaping plates; 404. a flow guide channel; 405. an electromagnetic valve.
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.
The fast curing epoxy resin system for the glass fiber pultrusion frame comprises the following components in parts by weight: 50-75 parts of polybutadiene epoxy resin, 50-75 parts of glycidyl ether type epoxy resin, 15-30 parts of modified toughening particles, 8-12 parts of a curing agent, 30-40 parts of liquid crystal epoxy resin, 25-30 parts of B144 epoxy resin, 10-20 parts of inorganic whiskers, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion, wherein the dendritic polymer comprises aromatic diisocyanate and G0 dendritic PAMAM, and the G0 dendritic PAMAM has a shell packaging structure with self-repairing performance and good strength performance through the interaction of a cross-linking structure and a chemically bonded interface with a polymer adhesive, so that the durability of the epoxy resin is effectively improved to achieve the optimal working strength, the high polymer waterproof emulsion is matched with machinery for shaping work, and has good adaptability and high stability, and comprises wear-resistant ceramic particle glue, emulsion and inorganic powder, the adhesive property of the raw materials of the epoxy resin system is improved through the high polymer waterproof emulsion, the durability of inorganic materials can be improved, the high polymer waterproof emulsion has the advantages of high compressive strength, rapid solidification and good adhesive property, and has good water retention property, crack resistance, high alkali resistance, ultraviolet resistance and the like, the high polymer waterproof emulsion is uniformly coated on the outer surface of the epoxy resin system, the wear-resistant ceramic particle glue in the high polymer waterproof emulsion has excellent toughness and shock resistance, and the wear-resistant ceramic particle glue adopts directional net reinforcement measures and further improves the toughness through coupling, so the fracture resistance and the toughness are strong, the damage and the peeling caused by impact force can be effectively prevented, on the other hand, because the ionic bond and the covalent bond thereof are strong bond bonds, the bond energy is higher, the influence of low temperature on the bond is small, the vibration frequency of the bond is extremely high, and the threat to the bond is difficult to be formed at normal temperature, the invention can not generate thermal shock damage, the existing glass fiber pultrusion frame needs to be continuously contacted with glass fiber for shaping in long-term work, and needs to be continuously moved, adjusted in position and carried out loading and unloading work in the work process, and the structure of the forming frame is unstable in long-term work, so that the work quality is gradually reduced.
Furthermore, the polybutadiene epoxy resin is a high molecular polymer formed by mixing epoxidized polybutadiene resin, E-51 epoxy resin 95% -70%, isocyanate, low molecular polyamide and modified amine curing agent, the polybutadiene epoxy resin has excellent electrical insulation performance, good thermal stability and chemical stability, the resistivity and dielectric property of EP resin can be obviously improved, active groups contained in the isocyanate can effectively connect EP and hydroxyl-terminated polybutadiene, the compatibility between two phases is increased, the impact strength of modified EP is greatly improved, the glycidyl ether type epoxy resin is a glycidyl ether polymer formed by condensation polymerization of ethylene glycol, glycerol, pentaerythritol, polyglycidyl and epichlorohydrin, and the glycidyl ether type epoxy resin not only retains the ultraviolet radiation resistance, ultraviolet radiation resistance, ultraviolet radiation resistance, ultraviolet radiation resistance, the curing agent has the characteristics of electric arc resistance and the like, overcomes the defects of brittleness and narrow selection of the type of the curing agent, has good comprehensive mechanical and electrical properties of the cured product, has a long service life after being mixed with the curing agent, can be widely applied to glass fiber forming work, and has wide application range and stable structure.
Furthermore, the modified toughening particles comprise rubber elastomers, core-shell polymers, thermoplastic resins, thermotropic liquid crystal polymers and nano particles, wherein the rubber elastomers comprise amino-terminated butadiene-acrylonitrile rubber and carboxyl-terminated butadiene-acrylonitrile rubber, the carboxyl-terminated butadiene-acrylonitrile rubber has nitrile groups with very high polarity and good molecular flexibility, a sea-island state micro phase separation structure which is beneficial to improving the toughness of the composite material is formed in a toughening EP system, different material components are respectively enriched in the core-shell polymer and the outside of the core-shell polymer, so that the core-shell polymer has different functions, the core-shell polymer has good flocculation property and is incompatible after being blended with EP, a complete sea-island state phase separation structure can be formed after curing, the toughness of the EP can be remarkably improved by controlling the components and the particle size of the core-shell polymer, and the strength can be kept for a long time after the glass fiber pultrusion forming frame is processed, after contacting with the glass fiber, the glass fiber has certain elasticity and keeps the stability of the frame body.
Furthermore, the liquid crystal epoxy resin is an epoxy resin obtained by introducing a monomer with a liquid crystal behavior in a reaction in the synthesis process of the epoxy resin, curing an epoxy compound in the temperature range of a liquid crystal phase monomer, performing isotropic to liquid crystal transition in the curing process of a system, and finally fixing the ordered arrangement of liquid crystal molecules by intermolecular crosslinking, wherein the liquid crystal epoxy resin has the characteristics of easy flowability of liquid and anisotropy such as birefringence of crystals and the like by using a smaller amount of the liquid crystal epoxy resin compared with the toughening of thermoplastic resin, wherein the liquid crystal is an intermediate state between isotropic liquid and completely ordered crystals, namely an oriented fluid which is not only easy to flow but also has the characteristics of anisotropy such as birefringence of the crystals and the like, in the liquid crystal epoxy resin system, the liquid crystal ordered region with spontaneous ordered orientation of crystal units is surrounded by the isotropic disordered region to form the heterogeneity of the liquid crystal epoxy resin, when an external force acts, the crazes appear in the isotropic disordered region firstly and spread along the direction of the external force, and when the crazes meet the liquid crystal ordered region, the crazes are blocked, so that the breaking strength of the liquid crystal epoxy resin is greatly improved.
Furthermore, the inorganic whiskers comprise zinc oxide whiskers, calcium sulfate whiskers, calcium carbonate whiskers and silicon carbide whiskers, the inorganic whiskers have a highly ordered atomic arrangement structure and can approach the theoretical strength of valence bonds among atoms, the potential of the epoxy adhesive is very high, the further expansion of microcracks can be prevented through crack deflection, crystal breaking, whisker pulling-out effect and crack bridging effect, the reinforced and toughened composite material has higher specific stiffness, specific strength, axial tensile strength, wear resistance and lower thermal expansion coefficient, and the high-performance resin material for the glass fiber forming frame needs to have the performances of high temperature resistance, higher strength, high wave permeability, wave absorption and the like, so the requirement can be effectively met by adopting the silicon carbide whisker toughened resin-based composite material, and the preparation method of the inorganic whiskers comprises the following steps:
the method comprises the following steps: simultaneously putting zinc oxide powder, calcium sulfate powder, calcium carbonate powder and silicon carbide powder into inorganic acid and stirring;
step two: introducing the sodium silicate solution into the inorganic acid mixed solution according to the ratio;
step three: adjusting the pH value of the mixed solution to 8-9;
step four: filtering the solution, and drying to obtain the inorganic crystal whisker.
Referring to fig. 1-4, a method for preparing a fast curing epoxy resin system for a glass fiber pultrusion frame includes the steps of:
s1: the polybutadiene epoxy resin weighed according to the proportion is prepared by introducing epoxidized polybutadiene resin, 95-70% of E-51 epoxy resin, isocyanate, low molecular polyamide and modified amine curing agent into a first reaction kettle 1 for mixing and then preparing high molecular polymer;
s2: mixing ethylene glycol, glycerol, pentaerythritol and polyglycidyl, introducing the mixture into a second reaction kettle 2, heating the mixture by a heater 201, introducing epoxy chloropropane during heating, and concentrating to obtain glycidyl ether type epoxy resin;
s3: adding a high molecular polymer, glycidyl ether type epoxy resin, 25-30 parts of B144 epoxy resin, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion into a third reaction kettle 3, heating to 135-140 ℃ under the protection of inert atmosphere, and carrying out heat preservation stirring reaction for 35-40 min;
s4: after the reaction, adding 15-30 parts of modified toughening particles, 10-20 parts of inorganic whiskers and 15-20 parts of dendritic polymers into a third reaction kettle 3, adjusting the temperature to 170-180 ℃, and continuously stirring for 3-8 hours;
s5: after stirring, adding 20-25 parts of high polymer waterproof emulsion and 8-12 parts of curing agent, adjusting the temperature to 120-130 ℃, stirring for 15-20 min, and performing rotary evaporation to remove organic matters to obtain epoxy resin;
s6: and (3) passing the epoxy resin through a forming frame mold 4 to prepare a glass fiber pultrusion forming frame mold with corresponding specification.
Further, the first reaction vessel 1 in S1 includes three material guiding hoppers 101, the three material guiding hoppers 101 are provided, the lower ends of the three material guiding hoppers 101 are all provided with weighing blanking valves 104, the upper end of the first reaction vessel 1 is provided with a sealing cover plate 105, the upper end of the sealing cover plate 105 is provided with a speed reducer 102 and a servo motor 103, the first reaction vessel 1 is internally provided with a first stirring paddle 109, the upper end of the first stirring paddle 109 is provided with a connecting shaft 110, the speed reducer 102 is in transmission connection with the servo motor 103, the speed reducer 102 is in transmission connection with the first stirring paddle 109 through the connecting shaft 110, the first reaction vessel 1 is externally provided with a protection ring 106, the three material guiding hoppers 101 are respectively filled with epoxidized polybutadiene resin, E-51 epoxy resin 95% -70%, isocyanate, low molecular polyamide and modified amine curing agent, weighing component blanking can be performed through the weighing blanking valves 104, can conveniently operate the raw materials variable, the first stirring rake 109 of accessible drives and stirs the mixture to the raw materials.
Further, two heaters 201 are arranged in S2, the two heaters 201 are respectively located on two sides of the inner lower end of the second reaction kettle 2, the lower ends of the second reaction kettle 2 and the first reaction kettle 1 are respectively provided with a feeding pipe 107, the lower end of the feeding pipe 107 is provided with a material guiding pipe 108, ethylene glycol, glycerol, pentaerythritol and polyethylene glycol are mixed by the second reaction kettle 2 and are heated by the heaters 201, and the high molecular polymer prepared by the first reaction kettle 1 and the glycidyl ether type epoxy resin prepared by the second reaction kettle 2 are respectively discharged through the two feeding pipes 107 and the material guiding pipe 108 for conveying.
Furthermore, an overhaul plate 302 is installed at the upper end of a third reaction kettle 3 in S3, a motor 301 is installed at the upper end of the overhaul plate 302, a second stirring paddle 304 is installed at the lower end of the motor 301, the motor 301 is in transmission connection with the second stirring paddle 304, a feeding pipe 303 is installed at the lower end of the third reaction kettle 3, two feeding pipes 108 extend into the third reaction kettle 3 and are in sealing connection with the third reaction kettle 3, a feeding hole 305 is formed at the upper end of the inside of the third reaction kettle 3, the feeding pipe 303 is installed below the front end of the third reaction kettle 3, the feeding pipes 108 can guide glycidyl ether type epoxy resin and high molecular polymer into the third reaction kettle 3, and 25-30 parts of B144 epoxy resin, 15-20 parts of dendritic polymer, 20-25 parts of high polymer waterproof emulsion, modified particle toughening, 10-20 parts of inorganic whisker, 15-20 parts of dendritic polymer, a, 20-25 parts of high polymer waterproof emulsion and 8-12 parts of curing agent are mixed by a second stirring paddle 304 in a third reaction kettle 3, so that the preparation work is convenient.
Further, shaping frame mould 4 in S6 includes shaping chamber 401 and design board 403, shaping chamber 401 sets up around design board 403, the upper end of design board 403 is provided with material receiving opening 402, the inside of material receiving opening 402 is provided with design board 403, and the inside of design board 403 is provided with water conservancy diversion passageway 404, the internally mounted of water conservancy diversion passageway 404 has solenoid valve 405, the position of conveying pipe 303 is corresponding with the position of material receiving opening 402, the epoxy system that makes is collected to accessible material receiving opening 402, through the inside water conservancy diversion passageway 404 of material receiving opening 402 with the epoxy water conservancy diversion, it becomes the pultrusion frame to finalize the design through shaping chamber 401, can conveniently regulate and control the epoxy component of each position of shaping chamber 401 through solenoid valve 405, and convenient regulation, and forming effects are improved.
In summary, according to the fast curing epoxy resin system for glass fiber pultrusion frame and the preparation method thereof, the epoxidized polybutadiene resin, the E-51 epoxy resin 95% -70%, the isocyanate, the low molecular polyamide and the modified amine curing agent are respectively put into the three material guiding hoppers 101, the weighing and weight blanking can be carried out through the weighing blanking valve 104, the raw material variables can be conveniently operated, the raw materials can be stirred and mixed under the driving of the first stirring paddle 109, the ethylene glycol, the glycerol, the pentaerythritol and the polyethylene glycol are mixed through the second reaction vessel 2, and the mixture is heated by the heater 201, the high molecular polymer prepared by the first reaction vessel 1 and the glycidyl ether type epoxy resin prepared by the second reaction vessel 2 are respectively discharged through the two material discharging pipes 107 and the material guiding pipes 108 for conveying, the material guiding pipes 108 can guide the glycidyl ether type epoxy resin and the high molecular polymer into the third reaction vessel 3, 25-30 parts of B144 epoxy resin, 15-20 parts of dendritic polymer, 20-25 parts of high polymer waterproof emulsion, modified toughening particles, 10-20 parts of inorganic whiskers, 15-20 parts of dendritic polymer, 20-25 parts of high polymer waterproof emulsion and 8-12 parts of curing agent can be introduced into a third reaction kettle 3 through a feed inlet 305, the materials are mixed through a second stirring paddle 304, the preparation work is convenient, the prepared epoxy resin system can be collected through a receiving port 402, the epoxy resin is guided through a guide channel 404 in the receiving port 402 and is shaped into a pultrusion forming frame through a forming cavity 401, the epoxy resin component of each position of the forming cavity 401 can be conveniently regulated through an electromagnetic valve 405, the regulation is convenient, the forming effect is improved, the formed epoxy resin system can resist breakage and has strong toughness, and the wear-resisting effect of the epoxy resin system is effectively improved by adding the high polymer waterproof emulsion and the dendritic polymer, the long-term mechanical connection is convenient, the glass fiber preparation work is carried out, and the working quality is effectively improved.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The fast curing epoxy resin system for the glass fiber pultrusion frame is characterized by comprising the following components in parts by weight: 50-75 parts of polybutadiene epoxy resin, 50-75 parts of glycidyl ether type epoxy resin, 15-30 parts of modified toughening particles, 8-12 parts of a curing agent, 30-40 parts of liquid crystal epoxy resin, 25-30 parts of B144 epoxy resin, 10-20 parts of inorganic whiskers, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion, wherein the dendritic polymer comprises aromatic diisocyanate and G0 dendritic PAMAM, and the high polymer waterproof emulsion comprises wear-resistant ceramic particle glue, emulsion and inorganic powder.
2. The rapid cure epoxy system for a glass fiber pultrusion frame of claim 1, wherein: the polybutadiene epoxy resin is a high-molecular polymer formed by mixing epoxidized polybutadiene resin, 95-70% of E-51 epoxy resin, isocyanate, low-molecular polyamide and a modified amine curing agent, and the glycidyl ether type epoxy resin is a glycidyl ether polymer formed by condensation polymerization of ethylene glycol, glycerol, pentaerythritol, polyglycidyl glycol and epoxy chloropropane.
3. The rapid cure epoxy system for a glass fiber pultrusion frame of claim 1, wherein: the modified toughening particles comprise rubber elastomers, core-shell polymers, thermoplastic resins, thermotropic liquid crystal polymers and nano particles, wherein the rubber elastomers comprise amino-terminated butadiene-acrylonitrile rubber and carboxyl-terminated butadiene-acrylonitrile rubber.
4. The rapid cure epoxy system for a glass fiber pultrusion frame of claim 1, wherein: the liquid crystal epoxy resin is obtained by introducing a monomer which can react to generate liquid crystal behavior in the synthesis process of the epoxy resin, curing an epoxy compound in the temperature range of the liquid crystal phase monomer, and converting the liquid crystal phase monomer from isotropy to liquid crystal property in the curing process of a system, wherein the ordered arrangement of liquid crystal molecules is finally fixed by intermolecular crosslinking.
5. The rapid cure epoxy system for a glass fiber pultrusion frame of claim 1, wherein: the inorganic crystal whisker comprises zinc oxide crystal whisker, calcium sulfate crystal whisker, calcium carbonate crystal whisker and silicon carbide crystal whisker, and the preparation method of the inorganic crystal whisker comprises the following steps:
the method comprises the following steps: simultaneously putting zinc oxide powder, calcium sulfate powder, calcium carbonate powder and silicon carbide powder into inorganic acid and stirring;
step two: introducing the sodium silicate solution into the inorganic acid mixed solution according to the ratio;
step three: adjusting the pH value of the mixed solution to 8-9;
step four: filtering the solution, and drying to obtain the inorganic crystal whisker.
6. The method of preparing a rapid cure epoxy system for a glass fiber pultrusion frame of claim 2, including the steps of:
s1: the polybutadiene epoxy resin weighed according to the proportion is prepared by introducing epoxidized polybutadiene resin, 95-70 percent of E-51 epoxy resin, isocyanate, low molecular polyamide and modified amine curing agent into a first reaction kettle (1) for mixing and then preparing high molecular polymer;
s2: mixing ethylene glycol, glycerol, pentaerythritol and polyglycidyl, introducing the mixture into a second reaction kettle (2) for heating through a heater (201), introducing epoxy chloropropane for concentrating during heating, and preparing glycidyl ether type epoxy resin;
s3: adding a high molecular polymer, glycidyl ether type epoxy resin, 25-30 parts of B144 epoxy resin, 15-20 parts of dendritic polymer and 20-25 parts of high polymer waterproof emulsion into a third reaction kettle (3), heating to 135-140 ℃ under the protection of inert atmosphere, and carrying out heat preservation stirring reaction for 35-40 min;
s4: after the reaction, adding 15-30 parts of modified toughening particles, 10-20 parts of inorganic whiskers and 15-20 parts of dendritic polymers into a third reaction kettle (3), adjusting the temperature to 170-180 ℃, and continuously stirring for 3-8 hours;
s5: after stirring, adding 20-25 parts of high polymer waterproof emulsion and 8-12 parts of curing agent, adjusting the temperature to 120-130 ℃, stirring for 15-20 min, and performing rotary evaporation to remove organic matters to obtain epoxy resin;
s6: and (3) passing the epoxy resin through a forming frame die (4) to prepare a glass fiber pultrusion forming frame die with corresponding specification.
7. The method of preparing a rapid cure epoxy system for a glass fiber pultrusion frame of claim 6, wherein: first reation kettle (1) in S1 includes guide hopper (101), guide hopper (101) are provided with threely, three the lower extreme of guide hopper (101) all is provided with unloading valve (104) of weighing, just sealed apron (105) are installed to the upper end of first reation kettle (1), speed reducer (102) and servo motor (103) are installed to the upper end of sealed apron (105), the internally mounted of first reation kettle (1) has first stirring rake (109), connecting axle (110) are installed to the upper end of first stirring rake (109), speed reducer (102) and servo motor (103) transmission are connected, just speed reducer (102) are connected with first stirring rake (109) transmission through connecting axle (110), the externally mounted of first reation kettle (1) has guard ring (106).
8. The method of preparing a rapid cure epoxy system for a glass fiber pultrusion frame of claim 7, wherein: the two heaters (201) in the S2 are arranged, the two heaters (201) are respectively located on two sides of the inner lower end of the second reaction kettle (2), the lower ends of the second reaction kettle (2) and the first reaction kettle (1) are respectively provided with a feeding pipe (107), and the lower end of the feeding pipe (107) is provided with a material guide pipe (108).
9. The method of preparing a fast curing epoxy resin system for glass fiber pultruded frames according to claim 8, wherein: maintenance board (302) are installed to the upper end of third reation kettle (3) in S3, motor (301) are installed to the upper end of maintenance board (302), second stirring rake (304) are installed to the lower extreme of motor (301), motor (301) are connected with second stirring rake (304) transmission, just conveying pipe (303), two are installed to the lower extreme of third reation kettle (3) guide pipe (108) all extend to third reation kettle (3) inside and third reation kettle (3) sealing connection, the inside upper end of third reation kettle (3) is provided with feed inlet (305), conveying pipe (303) are installed to the below of third reation kettle (3) front end.
10. The method of preparing a rapid cure epoxy system for a glass fiber pultrusion frame of claim 9, wherein: shaping frame mould (4) in S6 is including shaping chamber (401) and design board (403), shaping chamber (401) sets up around design board (403), the upper end of design board (403) is provided with material receiving opening (402), the inside of material receiving opening (402) is provided with design board (403), just the inside of design board (403) is provided with water conservancy diversion passageway (404), the internally mounted of water conservancy diversion passageway (404) has solenoid valve (405), the position of conveying pipe (303) is corresponding with the position of material receiving opening (402).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116574359A (en) * | 2023-06-20 | 2023-08-11 | 深圳市辉亚新材料科技有限公司 | Impact-resistant modified epoxy resin and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116574359A (en) * | 2023-06-20 | 2023-08-11 | 深圳市辉亚新材料科技有限公司 | Impact-resistant modified epoxy resin and preparation process thereof |
| CN116574359B (en) * | 2023-06-20 | 2024-03-26 | 深圳市辉亚新材料科技有限公司 | Impact-resistant modified epoxy resin and preparation process thereof |
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