CN115181396B - Preparation method of vinyl resin and composite material with controllable viscosity and gel time - Google Patents
Preparation method of vinyl resin and composite material with controllable viscosity and gel time Download PDFInfo
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- CN115181396B CN115181396B CN202210692053.9A CN202210692053A CN115181396B CN 115181396 B CN115181396 B CN 115181396B CN 202210692053 A CN202210692053 A CN 202210692053A CN 115181396 B CN115181396 B CN 115181396B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention discloses a vinyl resin with controllable viscosity and gel time and a preparation method of a composite material thereof, comprising the following steps: mixing vinyl resin and an auxiliary agent J to obtain a vinyl resin matrix; cooling the vinyl resin matrix to room temperature, sequentially adding an accelerator, an initiator, an auxiliary Z and an auxiliary C, and mixing to obtain a modified vinyl resin system with initial dynamic viscosity of 350-450 mPa.s and gel time of 10-240 min; vacuumizing and defoaming the modified vinyl resin system; and (3) layering the fiber cloth preform, and carrying out vacuum infusion on the defoamed vinyl resin, so as to obtain the vinyl resin-based composite material after solidification. The viscosity and the gel time of the prepared vinyl resin are controlled through the formula design, so that the vinyl resin is suitable for vacuum infusion process molding of products with different sizes and structures, meanwhile, the bonding strength between fiber cloth and resin is improved, and the vinyl resin-based composite material has excellent mechanical properties through the process design and the selection of a fiber cloth preform.
Description
Technical Field
The invention relates to a preparation method of resin and a composite material thereof, in particular to a preparation method of vinyl resin with controllable viscosity and gel time and a composite material thereof, belonging to the technical field of structural composite materials.
Background
The vinyl resin is prepared from unsaturated carboxylic acid and epoxy resin through ring-opening addition reaction, and has the advantages of good mechanical property, chemical corrosion resistance, rapid solidification and the like as internationally recognized highly corrosion-resistant resin, and the application of the vinyl resin is gradually expanded to the fields of traffic, ocean, oil fields and the like. Meanwhile, the vinyl ester resin has lower price, can effectively reduce the cost, and is a resin which is widely applied and researched after the epoxy resin.
The VARI, vacuum auxiliary resin permeation, is a low-cost manufacturing technology of composite materials developed in recent years, and relates to various fields of aerospace, weaponry, rail transit, marine ships and the like. In view of the advantages of the VARI technology in reducing the manufacturing cost of the composite material, various research institutions have developed in China since the beginning of the century, but the VARI preparation of the vinyl resin composite material does not achieve the ideal effect because the control process including the viscosity and the gel time of the resin is not mature enough, and the internal quality, the mechanical property and the like of the product are directly affected.
In addition, in recent years, research on carbon fiber reinforced vinyl resin matrix composite materials has attracted attention, and the aim is mainly to improve the interface combination of fibers and a resin matrix, thereby improving the mechanical properties of the composite materials. At present, most of carbon fibers sold in the market are coated with epoxy sizing agents, and good interfaces can be obtained for composite materials taking epoxy resin as a matrix, but for vinyl ester resin matrixes, free radical chain polymerization occurs during curing, and the mechanism of gradual ring-opening polymerization of epoxy groups of the epoxy resin is quite different, so that the epoxy sizing agents are not applicable any more, the interface performance of the composite materials is not improved well, and the interfaces become weak links of the carbon fiber reinforced vinyl ester resin composite materials.
Disclosure of Invention
The invention aims to overcome the defects, provides vinyl resin with controllable viscosity and gel time and a preparation method of a composite material thereof, and belongs to the technical field of structural composite materials. The method specifically comprises the following steps: mixing vinyl resin and an auxiliary agent J to obtain a vinyl resin matrix; cooling the vinyl resin matrix to room temperature, sequentially adding an accelerator, an initiator, an auxiliary agent Z and an auxiliary agent C, and mixing to obtain a modified vinyl resin system with initial dynamic viscosity of 350-450 mPa.s at 25 ℃ and gel time of 10-240 min; vacuumizing and defoaming the modified vinyl resin system; and (3) layering by using a fiber cloth preform, and carrying out vacuum infusion by using the defoamed vinyl resin, so as to obtain the vinyl resin-based composite material after solidification. The viscosity and the gel time of the prepared vinyl resin are controlled through the formula design, so that the vinyl resin is suitable for vacuum infusion process molding of products with different sizes and structures, meanwhile, the bonding strength between fiber cloth and resin is improved, and the prepared vinyl resin-based composite material has excellent mechanical properties through the process design and the selection of a fiber cloth preform.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing a vinyl resin with controllable viscosity and gel time, comprising:
(1) Mixing vinyl resin and an auxiliary agent J to obtain a vinyl resin matrix; the auxiliary agent J is a reactant of a silane coupling agent and diallyl bisphenol A epoxy resin or a reactant of bisphenol A polyether glycol, fumaric acid and adipic acid;
(2) Mixing a vinyl resin matrix with an accelerator to obtain a vinyl resin pre-promotion solution;
(3) Adding an initiator into the vinyl resin pre-promotion liquid to obtain a vinyl resin system;
(4) Mixing a vinyl resin system with an auxiliary Z and an auxiliary C to obtain a modified vinyl resin system; the auxiliary Z is one or more of hydroquinone, methyl hydroquinone or p-hydroxyanisole, and the auxiliary C is one or more of polyurea, polyacrylate or polyvinyl alcohol;
(5) And (3) vacuumizing and defoaming the modified vinyl resin system to obtain the vinyl resin with controllable viscosity and gel time.
A preparation method of a vinyl resin composite material with controllable viscosity and gel time comprises the following steps:
(1) Mixing vinyl resin and an auxiliary agent J to obtain a vinyl resin matrix; the auxiliary agent J is a reactant of a silane coupling agent and diallyl bisphenol A epoxy resin or a reactant of bisphenol A polyether glycol, fumaric acid and adipic acid;
(2) Mixing a vinyl resin matrix with an accelerator to obtain a vinyl resin pre-promotion solution;
(3) Adding an initiator into the vinyl resin pre-promotion liquid to obtain a vinyl resin system;
(4) Mixing a vinyl resin system with an auxiliary Z and an auxiliary C to obtain a modified vinyl resin system; the auxiliary Z is one or more of hydroquinone, methyl hydroquinone or p-hydroxyanisole, and the auxiliary C is one or more of polyurea, polyacrylate or polyvinyl alcohol;
(5) Vacuumizing and defoaming the modified vinyl resin system to obtain vinyl resin with controllable viscosity and gel time;
(6) And (3) after the fiber cloth is paved, vacuum infusion is carried out by adopting vinyl resin with controllable viscosity and gel time, and the vinyl resin composite material is obtained after solidification.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (1), the auxiliary agent J is a mixture of the components with the molar ratio of 1:1 to 1.1, the molar ratio of the silane coupling agent to the polycondensation reactant of the diallyl bisphenol A epoxy resin or the alkyd is 1:1 to 1.1 bisphenol a polyether glycol and fumaric acid and adipic acid;
in the step (1), vinyl resin and an auxiliary agent J are mixed at 30-45 ℃; in the step (1), the auxiliary agent J is granular, and the mass ratio of the vinyl resin to the auxiliary agent J is 99.5:0.5-97:3;
in the step (1), the vinyl resin is bisphenol type epoxy vinyl ester resin or phenolic epoxy type vinyl ester resin.
Further, in the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (2), the accelerator is one or more of copper metal compound, iron metal compound, manganese metal compound, cobalt metal compound, titanium metal compound and potassium metal compound;
in the step (2), the addition amount of the accelerator accounts for 0.05-2wt% of the mass of the vinyl resin matrix;
in the step (2), the vinyl resin matrix obtained in the step (1) is mixed with the accelerator after being brought to room temperature.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (3), the initiator is peroxide;
in the step (3), the addition amount of the initiator accounts for 0.8-2 wt% of the mass of the vinyl resin matrix.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (4), the addition amount of the auxiliary agent Z and the auxiliary agent C accounts for 0-0.025 wt% and 0.1-0.3 wt% of the mass percentage of the vinyl resin matrix respectively.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (5), the vacuumizing and defoaming treatment on the modified vinyl resin system is carried out in a closed pressure-bearing container, the vacuum pressure is 0.06-0.1 MPa, and the defoaming time is 5-15 min.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (6), after the fiber cloth preform is paved, a demolding material, a separation material, a diversion material and a vacuum bag film are sequentially coated, a glue injection pipeline, a suction pipeline and a glue blocking tape are arranged, then the vinyl resin with controllable viscosity and gel time is adopted for vacuum infusion, and the vinyl resin composite material is obtained after curing for 12-14 hours at 25+/-5 ℃;
in the step (6), the fiber cloth is E-glass fiber, S-glass fiber or carbon fiber fabric or stitch-bonded fabric coated with sizing agent on the surface; the surface density of the fiber cloth is 100-1300 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Carbon (C)The type of sizing agent coated on the surface of the fiber is aqueous epoxy sizing agent;
preferably, in the step (6), the surface density of the fiber cloth is 165-210 g/m 2 。
Further, in the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the preparation method further comprises the step (7):
and (3) performing post-curing treatment on the vinyl resin-based composite material obtained in the step (6), wherein the post-curing treatment conditions are as follows: heating to 120+/-5 ℃ at the heating rate of 60+/-5 ℃/h, preserving heat for 2h, and cooling to room temperature.
Further, in the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the viscosity and gel time of the vinyl resin and the bonding strength of the vinyl resin and the fiber cloth are controlled by controlling the proportion of the auxiliary agent J, the accelerator, the initiator, the auxiliary agent Z and the auxiliary agent C;
the initial dynamic viscosity of the vinyl resin with controllable viscosity and gel time obtained in the step (5) at 25 ℃ can be regulated and controlled within the range of 350-450 mPa.s, and the gel time can be regulated and controlled within the range of 10-240 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The modified vinyl resin system is innovatively obtained through formula design, is suitable for a low-cost manufacturing technology of the VARI composite material, aims at the size and structural characteristics of different formed components, and can control the low-viscosity maintenance time and the gel time of the resin by introducing the aid Z and the aid C through formula adjustment, so that the pouring time can be reasonably controlled, a proper operation window is ensured, the resin flow stability can be maintained, and the mechanical property of the vinyl resin composite material is effectively improved;
(2) According to the invention, through resin defoaming, air bubbles in the liquid resin are removed, the porosity of the composite material is reduced, and the internal quality is ensured; meanwhile, when in vacuum infusion, the pipeline and the adhesive tape are reasonably arranged, so that the defects of poor adhesive, loose composite material and the like caused by the phenomenon of excessive pumping of resin are avoided, and the product quality is improved;
(3) According to the invention, a certain proportion of auxiliary agent J is added into vinyl resin to adjust the interface performance of the resin and the fiber cloth preform, the preparation method of the composite material is suitable for different types of commercial fiber cloth, and can be used for preparing various composite material products meeting the mechanical property requirement, and the vinyl resin-based composite material prepared by the method has excellent mechanical property and comprehensive performance;
(4) The invention limits the proportion of the added auxiliary J, auxiliary Z and auxiliary C, so that the initial dynamic viscosity of the modified vinyl resin system at 25 ℃ is controllable within 350-450 mPa.s, the gel time is controllable within 10-240 min, and the modified vinyl resin system is suitable for vacuum infusion process molding of products with different sizes and structures;
(5) The preparation method disclosed by the invention is simple in process flow, easy to realize and high in practicability;
(6) The invention adopts a modified vinyl resin system with controllable viscosity and gel time, combines process design and fiber cloth preform selection, and the prepared vinyl resin-based composite material has excellent mechanical properties;
(7) The invention improves the interface combination of the fiber and the matrix by introducing the active functional group (bisphenol A skeleton structure and the like) which can react with the epoxy sizing agent and the vinyl resin, and further promotes the development and application of the carbon fiber reinforced vinyl resin matrix composite material.
Drawings
FIG. 1 is a typical viscosity-time graph of a vinyl resin with controllable viscosity and gel time according to the present invention;
FIG. 2 is a flow chart of a method for preparing a vinyl resin composite with controllable viscosity and gel time according to the present invention;
FIG. 3 is a schematic illustration of a typical lay-up structure for the preparation of a vinyl resin based composite material of the present invention;
FIG. 4 is a metallographic photograph of a composite material prepared according to example 1 of the present invention;
FIG. 5 is a metallographic photograph of a composite material prepared according to comparative example 1 of the present invention;
in the figure, 1-fiber cloth, 2-demolding material, 3-isolating material, 4-diversion material, 5-vacuum bag film, 6-air suction pipeline, 7-glue injection pipeline and 8-blocking tape.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
When the viscosity of the resin is too high, fluidity of the resin becomes poor, and infiltration of the resin into the fiber reinforcement becomes difficult; when the viscosity of the resin is too low, inter-bundle and intra-bundle flows of the resin in the reinforcing fiber body become unstable, and defects such as voids and interstices may occur in the article. In addition, the molding process needs to be completed within a low viscosity plateau time (process window) of the resin to avoid failure of the molding due to severe cross-linking curing reaction of the resin, so that a proper gel time is required. The viscosity and the gel time of the prepared vinyl resin are controlled through the formula design, so that the vinyl resin is suitable for vacuum infusion process molding of products with different sizes and structures, and the prepared vinyl resin-based composite material has excellent mechanical properties and comprehensive properties by combining the process design and the fiber cloth preform selection. The vinyl resin with controllable viscosity and gel time is suitable for VARI low-cost manufacturing technology, has good interface combination with the fiber modified by the aqueous epoxy sizing agent, has excellent mechanical properties of the corresponding composite material, and can be applied to the fields of ground weapon emission equipment, ships, wind power and the like.
Specifically, as shown in fig. 2, the preparation method of the vinyl resin composite material with controllable viscosity and gel time comprises the following steps:
(1) Mixing vinyl resin and the auxiliary agent J particles under the heating condition to obtain a vinyl resin matrix, wherein the mixing temperature is 30-45 ℃; wherein the mass ratio of the vinyl resin to the auxiliary agent J particles is 99.5:0.5-97:3; the mechanical properties of the prepared vinyl resin matrix composite can be controlled by adopting the auxiliary J with different proportions;
(2) Cooling the vinyl resin matrix obtained in the step (1) to room temperature, adding an accelerator, and mixing, wherein the addition amount of the accelerator is 0.05-2 wt% of the resin matrix, so as to obtain a vinyl resin pre-promotion liquid;
(3) Adding an initiator into the vinyl resin pre-solution obtained in the step (2) for mixing, wherein the addition amount of the initiator accounts for 0.8-2 wt% of the resin matrix, so as to obtain a vinyl resin system;
(4) Sequentially adding an auxiliary Z and an auxiliary C into the vinyl resin system obtained in the step (3) for mixing, wherein the addition accounts for 0-0.025 wt% and 0.1-0.3 wt% of the resin matrix respectively, so as to obtain a modified vinyl resin system;
(5) Placing the modified vinyl resin system obtained in the step (4) into a pressure-bearing container, sealing, and then carrying out vacuumizing and defoaming treatment, wherein the vacuum pressure is controlled to be 0.06-0.1 MPa, and the defoaming time is controlled to be 5-15 min;
(6) As shown in fig. 3, a fiber cloth 1 preform is used for paving, a demolding material 2, a separation material 3, a diversion material 4 and a vacuum bag film 5 are coated, a glue injection pipeline 7, a suction pipeline 6 and a blocking tape 8 are arranged, and then resin obtained in the step (5) is used for resin vacuum infusion to obtain a vinyl resin-based composite material, wherein the curing temperature is 25+/-5 ℃ and the curing time is 12-14 hours;
(7) And (3) performing post-curing treatment on the vinyl resin matrix composite cured at room temperature in the step (6), wherein the post-curing system is as follows: the temperature rising rate is 60+/-5 ℃/h, and the temperature is kept for 2 hours after reaching 120+/-5 ℃ and then the room temperature is reduced.
In the preparation method of the vinyl resin with controllable viscosity and gel time and the composite material thereof, the vinyl resin in the step (1) is bisphenol type vinyl ester resin or phenolic epoxy type vinyl ester resin.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, in the step (1), the auxiliary agent J particles are reactants of a silane coupling agent and diallyl bisphenol A epoxy resin or reactants of bisphenol A polyether glycol, fumaric acid and adipic acid, the auxiliary agent J is an interface modifier in the invention, so that the bonding strength between fiber cloth and resin can be effectively improved, the initiator is used for curing the resin, the accelerator plays a role in promoting the curing, the auxiliary agent Z, the initiator and the accelerator jointly regulate the gel time, the higher the addition amount of the auxiliary agent Z is, the longer the gel time is, the higher the addition amount of the initiator and the accelerator is, and the shorter the gel time is;
in the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the accelerator in the step (2) is selected from any one or combination of metal compounds of copper, iron, manganese, cobalt, titanium and potassium.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the initiator in the step (3) is peroxide.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the auxiliary agent Z in the step (4) is any one or combination of hydroquinone, methyl hydroquinone and p-hydroxyanisole. The addition agent Z is a polymerization inhibitor in the invention, so that the gel time can be adjusted, the amount of the polymerization inhibitor is increased, and the gel time is increased.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the auxiliary agent C in the step (4) is any one or combination of polyurea, polyacrylate or polyvinyl alcohol. The auxiliary agent C is a thixotropic agent in the invention, and is helpful for adjusting the viscosity of the resin, increasing the thixotropic amount and increasing the viscosity of the resin.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the initial dynamic viscosity of the vinyl resin prepared in the step (5) at 25 ℃ is 350-450 mPa.s, and the gel time is 10-240 min, namely the vinyl resin with controllable viscosity and gel time is obtained in the steps (1) - (5), and the vinyl resin is a typical viscosity-time curve chart of the vinyl resin disclosed by the invention as shown in figure 1.
In the preparation method of the vinyl resin with controllable viscosity and gel time and the composite material thereof, the fiber cloth in the step (5) is the fabric or stitch-bonded fabric of E-glass fiber, S-glass fiber or carbon fiber, and the surface density of the fiber cloth is 100-1300 g/m 2 Preferably T800 grade carbon fiber of Shanxi Steel carbon Material Co., ltd, preferably with an areal density of 165 to 210g/m 2 The type of carbon fiber sizing agent selected is an aqueous epoxy sizing agent.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the step (6) can be performed with post-curing treatment if necessary, and the mechanical property of the post-cured vinyl resin composite material is improved by more than 20%.
In the preparation method of the vinyl resin composite material with controllable viscosity and gel time, the viscosity and gel time of the prepared vinyl resin and the bonding strength with the fiber cloth preform are controlled by adding the auxiliary J, the accelerator, the initiator, the auxiliary Z and the auxiliary C in different proportions in the steps (1) - (4).
Example 1
Bisphenol type epoxy vinyl ester resin, silane coupling agent and diallyl bisphenol A epoxy resin reactant are mixed under the heating condition according to the proportion (mass ratio) of 97.5:2.5, and the mixing temperature is 40 ℃. The temperature is reduced to 25 ℃, and 0.1 percent (mass percent of the vinyl resin matrix) of cobalt compound, 0.8 percent (mass percent of the vinyl resin matrix) of methyl ethyl ketone peroxide, 0.02 percent (mass percent of the vinyl resin matrix) of hydroquinone and 0.2 percent (mass percent of the vinyl resin matrix) of polyurea are sequentially added;
and (3) placing the modified vinyl resin system into a pressure-bearing container, sealing, vacuumizing and defoaming, wherein the vacuum pressure is 0.1MPa, the defoaming time is 15min, and the minimum viscosity (namely, the initial dynamic viscosity at 25 ℃) of the modified vinyl resin system is 420 mPas, and the gel time is 180min.
T800 grade carbon fiber of Shanxi Steel carbon Material Co., ltd, with an areal density of 210g/m 2 The carbon fiber sizing agent type is an aqueous epoxy sizing agent.
Before laying, a mould air tightness experiment is first carried out: and laying an air guide material on the molding surface of the mold, coating the mold with the air guide material, vacuumizing until the pressure in the vacuum bag is less than or equal to-95 KPa, and maintaining the pressure for 5min, wherein the pressure rise is less than or equal to 0.5KPa. The mold meeting the conditions is allowed to be used.
And (3) performing fiber cloth laying and auxiliary material laying in the same manner, performing resin vacuum pouring after airtight sealing, closing a glue pouring pipeline after pouring, curing for 12 hours at 25+/-5 ℃ and then placing the mixture into an oven for post-curing treatment, wherein the post-curing system is that the temperature rise rate is 60 ℃/h, and cooling to room temperature after heat preservation is performed for 2 hours at 120+/-5 ℃.
The size of the composite material member obtained after curing is phi 2500 multiplied by 1800mm, the thickness is 5mm, the appearance is smooth, the defect inside the flaw detection is free, and the mechanical properties of the composite material are shown in Table 1:
table 1 test performance table for the composites obtained in the examples
As shown in fig. 4, which is a metallographic photograph of the experimental board of the composite material, the surface of the fiber is rough, and the bonding performance of the composite material and the fiber interface is good.
Comparative example 1
Adding cobalt compound 0.1% (in mass percent of the vinyl resin matrix), methyl ethyl ketone peroxide 0.8% (in mass percent of the vinyl resin matrix), hydroquinone 0.02% (in mass percent of the vinyl resin matrix) and polyurea 0.2% (in mass percent of the vinyl resin matrix) into bisphenol type epoxy vinyl ester resin in sequence.
And (3) placing the vinyl resin system into a pressure-bearing container, sealing, vacuumizing and defoaming, wherein the vacuum pressure is 0.1MPa, the defoaming time is 15min, and the modified vinyl resin system is obtained, the minimum viscosity (namely the initial dynamic viscosity at 25 ℃) is 420 mPas, and the gel time is 180min.
The fiber cloth is selected from T800 grade carbon fiber of Shanxi Steel carbon materials Co., ltd,the areal density is 210g/m 2 The carbon fiber sizing agent type is an aqueous epoxy sizing agent.
Before laying, a mould air tightness experiment is first carried out: and laying an air guide material on the molding surface of the mold, coating the mold with the air guide material, vacuumizing until the pressure in the vacuum bag is less than or equal to-95 KPa, and maintaining the pressure for 5min, wherein the pressure rise is less than or equal to 0.5KPa. The mold meeting the conditions is allowed to be used.
And (3) performing fiber cloth laying and auxiliary material laying in the same manner, performing resin vacuum pouring after airtight sealing, closing a glue pouring pipeline after pouring, curing for 12 hours at 25+/-5 ℃ and then placing the mixture into an oven for post-curing treatment, wherein the post-curing system is that the temperature rise rate is 60 ℃/h, and cooling to room temperature after heat preservation is performed for 2 hours at 120+/-5 ℃.
The size of the composite material member obtained after curing is phi 2500 multiplied by 1800mm, the thickness is 5mm, the appearance is smooth, the defect inside the flaw detection is free, and the mechanical properties of the composite material are shown in Table 2:
table 2 test performance table for the composite obtained in comparative example 1
| Testing performance | Comparative example 1 vinyl resin based composite |
| Tensile strength in machine direction/MPa | 583 |
| Longitudinal tensile modulus/GPa | 65.1 |
| Longitudinal compressive Strength/MPa | 234 |
| Longitudinal compression modulus/GPa | 56.8 |
| Flexural Strength in machine direction/MPa | 427 |
| Flexural modulus in the machine direction/GPa | 42.0 |
| Longitudinal interlaminar shear strength/MPa | 25.9 |
In this comparative example, no auxiliary J was added, and the properties of the resulting composite were significantly reduced, as compared with example 1. As can be seen from the metallographic photograph of the experimental plate of the composite material shown in fig. 5, the interface between the composite material and the fibers is smoother than that of fig. 4, which indicates that the composite material and the fibers cannot be bonded well.
Comparative example 2
Bisphenol type epoxy vinyl ester resin, silane coupling agent and diallyl bisphenol A epoxy resin reactant are mixed under the heating condition according to the proportion (mass ratio) of 97.5:2.5, and the mixing temperature is 40 ℃. The temperature is reduced to 25 ℃, and 0.1 percent (mass percent of the vinyl resin matrix) of cobalt compound, 0.8 percent (mass percent of the vinyl resin matrix) of methyl ethyl ketone peroxide and 0.2 percent (mass percent of the vinyl resin matrix) of polyurea are sequentially added.
And (3) placing the modified vinyl resin system into a pressure-bearing container, sealing, vacuumizing and defoaming, wherein the vacuum pressure is 0.1MPa, the defoaming time is 15min, and the minimum viscosity (namely, the initial dynamic viscosity at 25 ℃) of the modified vinyl resin system is 420 mPas, and the gel time is 80min.
T800 grade carbon fiber of Shanxi Steel carbon Material Co., ltd, with an areal density of 210g/m 2 The carbon fiber sizing agent type is an aqueous epoxy sizing agent.
Before laying, a mould air tightness experiment is first carried out: and laying an air guide material on the molding surface of the mold, coating the mold with the air guide material, vacuumizing until the pressure in the vacuum bag is less than or equal to-95 KPa, and maintaining the pressure for 5min, wherein the pressure rise is less than or equal to 0.5KPa. The mold meeting the conditions is allowed to be used.
And (3) performing fiber cloth laying and auxiliary material laying in the same way as the above, keeping air tightness, performing resin vacuum infusion, and after the gel time of a resin system is too short, performing laying-infusion-curing for 2-3 times, closing an adhesive injection pipeline after the infusion is completed, curing for 12 hours at 25+/-5 ℃, then placing the adhesive in an oven for post-curing treatment, wherein the post-curing system is that the temperature rise rate is 60 ℃/h, and after the temperature reaches 120+/-5 ℃, preserving the heat for 2 hours, and then cooling to room temperature.
The dimensions of the composite material member obtained after curing were 2500X 1800mm, the thickness was 5mm, the appearance was smooth, the flaw detection was free from defects, and compared with example 1, no auxiliary Z was added in this comparative example, and the mechanical properties and metallographic photographs of the obtained composite material were substantially the same as those of Table 1 and FIG. 4, but the molding cycle was prolonged by 2 to 3 times.
Comparative example 3
Bisphenol type epoxy vinyl ester resin, silane coupling agent and diallyl bisphenol A epoxy resin reactant are mixed under the heating condition according to the proportion (mass ratio) of 97.5:2.5, and the mixing temperature is 40 ℃. The temperature is reduced to 25 ℃, and 0.1 percent (mass percent of the vinyl resin matrix) of cobalt compound, 0.8 percent (mass percent of the vinyl resin matrix) of methyl ethyl ketone peroxide and 0.02 percent (mass percent of the vinyl resin matrix) of hydroquinone are sequentially added.
And (3) placing the modified vinyl resin system into a pressure-bearing container, sealing, vacuumizing and defoaming, wherein the vacuum pressure is 0.1MPa, the defoaming time is 15min, and the minimum viscosity (namely, the initial dynamic viscosity at 25 ℃) of the modified vinyl resin system is 240 mPas, and the gel time is 180min.
T800 grade carbon fiber of Shanxi Steel carbon Material Co., ltd, with an areal density of 210g/m 2 The carbon fiber sizing agent type is an aqueous epoxy sizing agent.
Before laying, a mould air tightness experiment is first carried out: and laying an air guide material on the molding surface of the mold, coating the mold with the air guide material, vacuumizing until the pressure in the vacuum bag is less than or equal to-95 KPa, and maintaining the pressure for 5min, wherein the pressure rise is less than or equal to 0.5KPa. The mold meeting the conditions is allowed to be used.
And (3) performing fiber cloth laying and auxiliary material laying in the same manner, performing resin vacuum pouring after airtight sealing, closing a glue pouring pipeline after pouring, curing for 12 hours at 25+/-5 ℃ and then placing the mixture into an oven for post-curing treatment, wherein the post-curing system is that the temperature rise rate is 60 ℃/h, and cooling to room temperature after heat preservation is performed for 2 hours at 120+/-5 ℃.
The size of the composite material member obtained after curing is phi 2500 x 1800mm, the thickness is 5mm, and compared with the comparative example 1, the mechanical property and metallographic photograph of the obtained composite material are basically consistent with those of the table 1 and the table 4, but the appearance local fiber lines are obvious, the defect detection local has the phenomenon of poor glue, and the severe occurrence of loose is caused because the viscosity in the comparative example is not well controlled, so that the molding quality is poor.
In conclusion, the composite material with good mechanical properties, short molding cycle and excellent quality can be obtained by adding the three auxiliary agents, and meanwhile, the three auxiliary agents have synergistic effects.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (10)
1. A method for preparing a vinyl resin with controllable viscosity and gel time, comprising:
(1) Mixing vinyl resin and an auxiliary agent J to obtain a vinyl resin matrix; the auxiliary agent J is a reactant of a silane coupling agent and diallyl bisphenol A epoxy resin or a reactant of bisphenol A polyether glycol, fumaric acid and adipic acid;
(2) Mixing a vinyl resin matrix with an accelerator to obtain a vinyl resin pre-promotion solution;
(3) Adding an initiator into the vinyl resin pre-promotion liquid to obtain a vinyl resin system;
(4) Mixing a vinyl resin system with an auxiliary Z and an auxiliary C to obtain a modified vinyl resin system; the auxiliary Z is one or more of hydroquinone, methyl hydroquinone or p-hydroxyanisole, and the auxiliary C is one or more of polyurea, polyacrylate or polyvinyl alcohol;
(5) And (3) vacuumizing and defoaming the modified vinyl resin system to obtain the vinyl resin with controllable viscosity and gel time.
2. The method for producing a vinyl resin with controllable viscosity and gel time according to claim 1, wherein in the step (1), the auxiliary J is a molar ratio of 1: 1-1.1 of a polycondensation reactant of a silane coupling agent and diallyl bisphenol A epoxy resin or alkyd, wherein the molar ratio of the polycondensation reactant to the alkyd is 1: 1-1.1 of a polycondensation reactant of bisphenol A polyether glycol and fumaric acid and adipic acid;
in the step (1), vinyl resin and an auxiliary agent J are mixed at 30-45 ℃; in the step (1), the auxiliary agent J is granular, and the mass ratio of the vinyl resin to the auxiliary agent J is 99.5:0.5-97:3;
in the step (1), the vinyl resin is bisphenol type epoxy vinyl ester resin or phenolic epoxy type vinyl ester resin.
3. The method for producing a vinyl resin with controllable viscosity and gel time according to claim 1, wherein in the step (2), the accelerator is one or a combination of more than one of a metal compound of copper, a metal compound of iron, a metal compound of manganese, a metal compound of cobalt, a metal compound of titanium, and a metal compound of potassium;
in the step (2), the addition amount of the accelerator accounts for 0.05-2wt% of the mass of the vinyl resin matrix;
in the step (2), the vinyl resin matrix obtained in the step (1) is mixed with the accelerator after being brought to room temperature.
4. The method for producing a vinyl resin having a controllable viscosity and gel time according to claim 1, wherein in the step (3), the initiator is a peroxide;
in the step (3), the addition amount of the initiator accounts for 0.8-2wt% of the mass of the vinyl resin matrix.
5. The method for preparing vinyl resin with controllable viscosity and gel time according to claim 1, wherein in the step (4), the addition amount of the auxiliary agent Z and the auxiliary agent C accounts for 0-0.025 wt% and 0.1-0.3 wt% of the mass of the vinyl resin matrix respectively.
6. The method for preparing vinyl resin with controllable viscosity and gel time according to claim 1, wherein in the step (5), the vacuumizing and defoaming treatment on the modified vinyl resin system is performed in a closed pressure-bearing container, the vacuum pressure is 0.06-0.1 MPa, and the defoaming time is 5-15 min.
7. A method for preparing a vinyl resin composite material with controllable viscosity and gel time, comprising the steps of:
after the fiber cloth is paved, vinyl resin with controllable viscosity and gel time is adopted for vacuum infusion, and the vinyl resin composite material is obtained after solidification; the vinyl resin with controllable viscosity and gel time is a vinyl resin obtained by the preparation method of the vinyl resin with controllable viscosity and gel time according to any one of claims 1 to 6.
8. The method for preparing the vinyl resin composite material with controllable viscosity and gel time according to claim 7, wherein after the fiber cloth preform is paved, a demolding material, an isolating material, a diversion material and a vacuum bag film are sequentially coated, a glue injection pipeline, a suction pipeline and a blocking tape are arranged, then the vinyl resin with controllable viscosity and gel time is adopted for vacuum infusion, and the vinyl resin composite material is obtained after curing for 12-14 hours at 25+/-5 ℃;
the fiber cloth is E-glass fiber, S-glass fiber or carbon fiber fabric or stitch-bonded fabric coated with sizing agent on the surface; the surface density of the fiber cloth is 100-1300 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The type of sizing agent applied to the surface of the carbon fiber is an aqueous epoxy sizing agent.
9. The method for preparing a vinyl resin composite with controllable viscosity and gel time as claimed in claim 7, further comprising the steps of:
post-curing the vinyl resin composite material obtained after curing, wherein the post-curing conditions are as follows: heating to 120+/-5 ℃ at the heating rate of 60+/-5 ℃/h, preserving heat for 2h, and cooling to room temperature.
10. The method for preparing a vinyl resin composite material with controllable viscosity and gel time according to any one of claims 7 to 9, wherein the viscosity, gel time and bonding strength of the vinyl resin and the fiber cloth are controlled by controlling the proportion of the auxiliary agent J, the accelerator, the initiator, the auxiliary agent Z and the auxiliary agent C;
the initial dynamic viscosity of the vinyl resin with controllable viscosity and gel time at 25 ℃ can be regulated and controlled within the range of 350-450 mPa.s, and the gel time can be regulated and controlled within the range of 10-240 min.
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| KR20220007438A (en) * | 2020-07-10 | 2022-01-18 | 효성첨단소재 주식회사 | Non-solvent hotmelt type vinylester based high speed curing resin composition and manufacturing method thereof |
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| US4931514A (en) * | 1986-10-06 | 1990-06-05 | Waters William D | Admixing metal salt promotor, initiator and (m)ethyl acetoacetate to cure vinyl esters |
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