CN110283278B - Polydicyclopentadiene composite material and preparation method thereof - Google Patents
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Abstract
The invention relates to a polydicyclopentadiene composite material and a preparation method thereof, belonging to the field of polymer composite materials, wherein the composite material is obtained by reacting a raw material composition, the raw material composition comprises dicyclopentadiene, modified silicon dioxide and a catalyst, when the dicyclopentadiene in the raw material composition is taken as 100 parts by mass, the modified silicon dioxide is 0.01-2 parts by mass, the catalyst is 0.01-0.5 part by mass, the modified silicon dioxide is silicon dioxide containing ethyl and vinyl, and the catalyst is a first-generation Grubbs catalyst or a second-generation Grubbs catalyst. The prepared polydicyclopentadiene composite material has high tensile strength, tensile toughness and impact toughness, the addition amount of the modified silica is small, the efficiency is high, and compared with 100 parts by mass of dicyclopentadiene, the yield strength of 15%, the tensile toughness of 500% and the impact toughness of 100% can be improved by only filling a small amount of the modified silica, such as 0.1-0.2 part by mass of the modified silica.
Description
Technical Field
The invention relates to a thermosetting polymer matrix composite material, in particular to a silicon dioxide/polydicyclopentadiene composite material and a preparation method thereof.
Background
Polydicyclopentadiene (PDCPD) is an engineering plastic with impact resistance and modulus polymerized by monomer dicyclopentadiene under the action of a catalyst, and the monomer dicyclopentadiene is a byproduct with larger yield in the production of petrochemical ethylene.
The polydicyclopentadiene engineering plastic has the characteristics of good heat resistance, creep resistance, dimensional stability, shape memory, corrosion resistance, light weight and the like, and can be used for manufacturing various high-performance, high-added-value and high-grade fine products. Such as: automobile bumpers, guard plates, side plates, engine covers, automobile body shells and the like in the transportation industry; housings for large-sized electrical devices such as motors and air conditioners in electrical devices; parts of snowmobiles, surfboards, golf carts, etc. in sports equipment, agricultural machinery, civil engineering and construction materials, etc. The industrial production of polydicyclopentadiene has been realized in countries such as the United states, Japan, Europe, etc., and the current production of polydicyclopentadiene abroad adopts the processes of Reaction Injection Molding (RIM) and Resin Transfer Molding (RTM), and both of the processes have the advantages of high molding speed, low processing temperature, low injection pressure, etc. Because the polydicyclopentadiene is a thermosetting resin and has the general characteristics of the thermosetting resin, the pure polydicyclopentadiene cannot meet the requirements of the special engineering fields such as the automobile field, the building template and the like in the aspects of impact toughness and yield strength.
Silicon dioxide (SiO)2) The powder is white powder with low cost, no toxicity, no pollution, light weight and a microstructure similar to a sphere, has a high specific surface area, can be reduced to a nanometer level in particle size, and is an excellent reinforcing material. Due to pure SiO2The surface has a large amount of polar hydroxyl (-OH) groups, and the compatibility and dispersibility with a nonpolar DCPD interface are poor, so that SiO is required2Nonpolar groups are introduced on the surface to increase DCPD monomer and SiO2Interface compatibility and dispersibility of (A) to (B), which is to realize SiO2The key to PDCPD enhancement. Chinese patent CN106632776A (earlier research by the inventor) discloses a method for preparing polydicyclopentadiene composite material, which adds silicon dioxide with nonpolar group to realize the reinforcement and toughening of polydicyclopentadiene composite material.
Disclosure of Invention
In chinese patent CN106632776A, the effect of improving tensile strength and tensile toughness is achieved by adding nonpolar group silica. However, in the practical application of composite materials, yield strength and impact toughness are of great importance and are not mentioned in the patent literature. Later experiments of the inventor prove that the silicon dioxide with a single nonpolar group can effectively improve the yield strength, the tensile toughness and the impact toughness, and is very challenging.
Accordingly, it is an object of the present invention to provide polydicyclopentadiene composites having high yield strength, high tensile toughness, and high impact toughness.
The inventors of the present invention have conducted extensive studies and finally found that: meanwhile, the modified silicon dioxide containing ethyl and vinyl has good interface compatibility and dispersibility in dicyclopentadiene, and then polydicyclopentadiene composite material is prepared through in-situ polymerization.
Namely, the polydicyclopentadiene composite material is obtained by reacting raw material compositions, and is characterized in that: the raw material composition comprises dicyclopentadiene, modified silicon dioxide and a catalyst, wherein when the dicyclopentadiene in the raw material composition is taken as 100 parts by mass, the modified silicon dioxide is 0.01-2 parts by mass, the catalyst is 0.01-0.5 part by mass, the modified silicon dioxide is silicon dioxide containing ethyl and vinyl, and the catalyst is a first-generation Grubbs catalyst or a second-generation Grubbs catalyst.
Further, the average diameter of the modified silica was 100-1500 nm.
Further, the modified silica is contained in an amount of 0.01 to 0.5 part by mass based on 100 parts by mass of dicyclopentadiene.
Further, the total content of vinyl groups and ethyl groups is 5 to 20 parts by mass per 100 parts by mass of the modified silica.
Furthermore, the preparation method of the polydicyclopentadiene composite material comprises the step (1) and the step (2),
step (1): preparing modified silicon dioxide;
step (2): and (2) uniformly mixing dicyclopentadiene, a catalyst and the modified silicon dioxide obtained in the step (1), and carrying out in-situ polymerization to obtain the polydicyclopentadiene composite material.
Furthermore, the preparation method of the polydicyclopentadiene composite material comprises the step (1) of synthesizing the modified silicon dioxide by using a silane coupling agent containing vinyl and a silane coupling agent containing ethyl in one step by adopting a sol-gel method.
Compared with the prior art, the invention has the following advantages:
the modified silicon dioxide prepared by the method has high purity, and the dispersibility and the interface compatibility of the modified silicon dioxide and the dicyclopentadiene monomer are effectively improved; the prepared polydicyclopentadiene composite material has high yield strength, tensile toughness and impact toughness; the preparation method is simple to operate, the addition amount of the modified silica and the catalyst is small, the efficiency is high, the industrial production is easy, and compared with 100 parts by mass of dicyclopentadiene, the yield strength of more than 15%, the tensile toughness of more than 500% and the impact toughness of more than 100% can be simultaneously improved by only filling a small amount of modified silica, such as 0.1-0.2 parts by mass of modified silica.
Drawings
FIG. 1 is a scanning electron micrograph of the modified silica prepared in example 1.
FIG. 2 scanning electron micrograph of the impact section: a) pure polydicyclopentadiene; b) example 2 the resulting modified silica/polydicyclopentadiene composite was prepared; c) comparative example 1 the resulting vinyl silica/polydicyclopentadiene composite was prepared; d) comparative example 2 the resulting ethyl silica/polydicyclopentadiene composite was prepared.
Detailed Description
The present invention will be described in detail below.
The polydicyclopentadiene composite material is obtained by reacting raw material compositions, and is characterized in that: the raw material composition comprises dicyclopentadiene, modified silicon dioxide and a catalyst, wherein when the dicyclopentadiene in the raw material composition is taken as 100 parts by mass, the modified silicon dioxide is 0.01-2 parts by mass, the catalyst is 0.01-0.5 part by mass, the modified silicon dioxide is silicon dioxide containing ethyl and vinyl, and the catalyst is a first-generation Grubbs catalyst or a second-generation Grubbs catalyst.
The average diameter of the modified silica is not particularly limited, and is usually 100-1500 nm. Considering that the particle size of the silicon dioxide is too small and easy to agglomerate, the dispersibility in the matrix is poor; the particle size is too large to bridge microcracks or cavities formed in the stretching process, so that the reinforcing and toughening effects are reduced, and the average diameter of the silicon dioxide is preferably 300-1000 nm.
The average diameter of the modified silica may be measured by a scanning electron microscope or a laser particle sizer, and when measured by a scanning electron microscope, the modified silica is analyzed by Image Pro-plus software, 100 sample microspheres are selected in an SEM photograph and the diameters thereof are measured, and then the average diameter is obtained by averaging.
The raw material composition of the present invention contains the modified silica in an amount of 0.01 to 2 parts by mass per 100 parts by mass of dicyclopentadiene. The amount of silica added is preferably 0.01 to 0.5 parts by mass, in view of the tendency of agglomeration of the modified silica to occur and the occurrence of stress concentration during stretching to cause fracture of the material.
The total content of the vinyl group and the ethyl group in the modified silica is not particularly limited, and the total content of the vinyl group and the ethyl group is 5 to 20 parts by mass with respect to 100 parts by mass of the modified silica.
The preparation method of the polydicyclopentadiene composite material comprises the steps (1) and (2),
step (1): preparing modified silicon dioxide;
step (2): and (2) uniformly mixing dicyclopentadiene, a catalyst and the modified silicon dioxide obtained in the step (1), and carrying out in-situ polymerization to obtain the polydicyclopentadiene composite material.
The preparation method of the polydicyclopentadiene composite material comprises the step (1) of synthesizing modified silicon dioxide by using a silane coupling agent containing vinyl and a silane coupling agent containing ethyl in one step by adopting a sol-gel method.
The silane coupling agent containing vinyl is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl (2-methoxyethoxy) silane, vinyl triisopropoxy silane, vinyl triacetoxy silane, allyl trimethoxy silane, allyl triethoxy silane, styrene ethyl trimethoxy silane, phenyl trimethoxy silane and phenyl triethoxy silane, and the silane coupling agent containing ethyl is one or two of ethyl trimethoxy silane and ethyl triethoxy silane.
[ step (1): preparation of modified silica ]
Adding a silane coupling agent containing vinyl and a silane coupling agent containing ethyl into a polar solvent, and violently stirring for 0.5-5h at 20-40 ℃ until clear and transparent mixed liquor is obtained; then adding ammonia water into the mixed solution, and stirring and reacting for 2-8h at 20-60 ℃ to obtain uniform milky mixed solution; centrifuging the mixed solution at the centrifugation revolution of 5000-.
The amounts of the two silane coupling agents, the polar solvent and the aqueous ammonia are not particularly limited, but the amount of the two silane coupling agents is usually 5 to 50mL, preferably 5 to 20mL, and the amount of the aqueous ammonia is 5 to 50mL, preferably 20 to 40mL, based on 1L of the polar solvent.
The volume ratio of the silane coupling agent containing vinyl to the silane coupling agent containing ethyl in the two silane coupling agents can be 5: 1-1: 5, preferably 1: 1, and in the range, the particle size of the prepared modified silica is uniform, and the contents of the functional groups of ethyl and vinyl are balanced.
The polar solvent used in the step (1) is not particularly limited, and may be one of distilled water and ethanol or a mixed solution of both.
Step (2): uniformly mixing dicyclopentadiene, a catalyst and the modified silicon dioxide obtained in the step (1), and carrying out in-situ polymerization to obtain the polydicyclopentadiene composite material
Adding the modified silicon dioxide obtained in the step (1) into liquid dicyclopentadiene, performing ultrasonic dispersion to obtain a uniformly dispersed mixed solution, adding a catalyst and dichloromethane mixed solution into the solution, uniformly stirring at room temperature, quickly injecting into a mold, and curing to obtain the polydicyclopentadiene composite material.
In the step (2), the addition amount of the modified silica is 0.01 to 2 parts by mass, preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of dicyclopentadiene.
The catalyst in the step (2) is a first-generation Grubbs catalyst and a second-generation Grubbs catalyst, and the first-generation Grubbs catalyst is preferred in view of the use conditions and the cost of the two catalysts. The amount of the catalyst added is 0.01 to 0.5 part by mass per 100 parts by mass of dicyclopentadiene. When preparing a mixed solution of the catalyst and dichloromethane, dichloromethane is not particularly limited, and the amount of dichloromethane added is usually 0.1 to 0.5 ml.
The room temperature in the step (2) is 25-35 ℃.
The curing process in the step (2) is 0.5-2h at 50-70 ℃, 0.5-2h at 90-110 ℃ and 0.5-2h at 150-170 ℃.
Examples
Hereinafter, the present invention will be described more specifically by the following examples. The examples are provided herein for illustrative purposes only and should not be construed as limiting the scope of the invention. The present invention may be carried out with various changes and modifications without departing from the spirit and scope thereof. Such changes and modifications are to be understood as being within the purview of the appended claims and are to be construed as part of the present invention. Wherein, the related raw materials of the silane coupling agent, the dicyclopentadiene and the catalyst are all commercial products.
Example 1
Placing 5mL of vinyl trimethoxy silane, 5mL of ethyl trimethoxy silane and 1L of distilled water in a reaction vessel, and stirring at 40 ℃ for 4 hours to fully hydrolyze a silane coupling agent to obtain a clear and transparent mixed solution A; adding 25mL of ammonia water into the solution A, and reacting at 50 ℃ for 6 hours to obtain a uniform milky mixed solution B; centrifuging the solution B for 5min at the speed of 5000r/min to obtain white solid, washing the white solid with distilled water and ethanol twice, and vacuum drying at 60 deg.C for 6 hr to obtain white powder, which is shown in FIG. 1. The average diameter of the modified silica was measured by scanning electron microscopy and laser granulometry to be 520 nm; the total vinyl and ethyl content of the vinyl silica was about 12.9% as determined by thermogravimetric analysis.
Placing 0.1g of modified silicon dioxide and 100mL of liquid dicyclopentadiene (purchased from carbofuran technologies, Inc.) in a 500mL round-bottom flask, and performing ultrasonic dispersion for 30min to obtain a uniform mixed solution C; 0.09g of a one-generation Grubbs catalyst (from Sigma-Aldrich) was weighed out, followed by 2mL of CH2Cl2Dissolving a catalyst to obtain a mixed solution D; and adding the solution D into the solution C, uniformly stirring at room temperature, quickly injecting into a tensile sample band mold, heating for curing, and obtaining the polydicyclopentadiene composite material after 1 hour at 70 ℃, 1 hour at 110 ℃ and 1 hour at 150 ℃.
The pure polydicyclopentadiene is prepared as follows; 100mL of liquid dicyclopentadiene is put into 500mL of round bottom to be sinteredIn a bottle; 0.10g of a first-generation Grubbs catalyst was weighed out and 2mL of CH was used2Cl2Dissolving a catalyst to obtain a mixed solution D; adding the solution D into the round-bottom flask, uniformly stirring at room temperature, quickly injecting into a tensile sample bar mold, heating for curing, and obtaining pure polydicyclopentadiene at 70 ℃ for 1h, 110 ℃ for 1h and 150 ℃ for 1 h.
And (4) carrying out tensile test on the sample strip by using a universal testing machine to obtain a stress-strain curve, and obtaining the tensile toughness of the composite material by integrating the curve. Compared with the pure polydicyclopentadiene material, the yield strength is improved from 36MPa to 42MPa, and the tensile toughness is improved from 2.53MPa to 15.7 MPa. The impact toughness is obtained by the notch impact strength of the cantilever beam through the test of an impact tester, and compared with a pure polydicyclopentadiene material, the impact toughness is 2.01KJ/m2Increased to 4.12KJ/m2。
Example 2
The modified silica was prepared in the same manner as in example 1. The same procedure as in example 1 was repeated except that the amount of modified silica added was changed from 0.1g to 0.2 g. The prepared polydicyclopentadiene material has the following mechanical test effects:
the yield strength is improved from 36MPa to 46MPa, and the tensile toughness is improved from 2.53MPa to 24.3 MPa. The impact toughness is from 2.19KJ/m2Increased to 4.46KJ/m2。
Comparative example 1
Placing 10mL of vinyl trimethoxy silane and 1L of distilled water in a reaction vessel, and stirring for 4 hours at 40 ℃ to fully hydrolyze a silane coupling agent to obtain a clear and transparent mixed solution A; adding 25mL of ammonia water into the solution A, and reacting at 50 ℃ for 6 hours to obtain a uniform milky mixed solution B; and centrifuging the solution B for 5min at the revolution of 5000r/min to obtain a white solid, washing the white solid with distilled water and ethanol respectively twice in sequence, and finally drying in vacuum at 60 ℃ for 6h to obtain white powder, namely the vinyl silicon dioxide. The average diameter of the vinyl silica was 410nm as measured by a scanning electron microscope and a laser particle sizer; the vinyl content of the vinyl silica was about 4.33% as determined by thermogravimetric analysis.
Placing 0.2g of vinyl silicon dioxide and 100mL of liquid dicyclopentadiene (purchased from carbofuran technologies, Inc.) in a 500mL round-bottom flask, and performing ultrasonic dispersion for 30min to obtain a uniform mixed solution C; 0.10g of a first-generation Grubbs catalyst was weighed out and 2mL of CH was used2Cl2Dissolving a catalyst to obtain a mixed solution D; and adding the solution D into the solution C, uniformly stirring at room temperature, quickly injecting into a tensile sample band mold, heating for curing, and obtaining the polydicyclopentadiene composite material after 1 hour at 70 ℃, 1 hour at 110 ℃ and 1 hour at 150 ℃.
Compared with the pure polydicyclopentadiene material, the yield strength is improved from 36MPa to 38MPa, and the tensile toughness is improved from 2.53MPa to 24.8 MPa. The impact toughness is obtained by the notched impact strength of the cantilever beam through the test of an impact tester, and compared with a pure polydicyclopentadiene material, the impact toughness is only 2.19KJ/m2Increased to 2.79KJ/m2The lifting effect is not obvious.
Comparative example 2
Placing 10mL of ethyl trimethoxy silane and 1L of distilled water in a reaction container, and stirring for 4 hours at 40 ℃ to fully hydrolyze a silane coupling agent to obtain a clear and transparent mixed solution A; adding 25mL of ammonia water into the solution A, and reacting at 50 ℃ for 6 hours to obtain a uniform milky mixed solution B; and centrifuging the solution B for 5min at the speed of 5000r/min to obtain a white solid, washing the white solid twice with distilled water and ethanol in sequence, and finally drying in vacuum at 60 ℃ for 6h to obtain white powder, namely the ethyl silicon dioxide. The average diameter of the ethyl silicon dioxide measured by a scanning electron microscope and a laser particle sizer was 370 nm; the vinyl content of the vinyl silica was about 24.5% as determined by thermogravimetric analysis.
Placing 0.2g of ethyl silicon dioxide and 100mL of liquid dicyclopentadiene (purchased from carbofuran technologies, Inc.) in a 500mL round-bottom flask, and performing ultrasonic dispersion for 30min to obtain a uniform mixed solution C; 0.10g of a first-generation Grubbs catalyst was weighed out and 2mL of CH was used2Cl2Dissolving a catalyst to obtain a mixed solution D; adding the solution D into the solution C, stirring uniformly at room temperature, quickly injecting into a tensile sample bar mold, heating for curing at 70 ℃ for 1h and at 110 ℃ for 1h,and (4) obtaining the polydicyclopentadiene composite material after 1h at the temperature of 150 ℃.
Compared with pure polydicyclopentadiene material, the yield strength is improved from 36MPa to 44MPa, and the tensile toughness is improved from 2.53MPa to 6.39 MPa. Compared with pure polydicyclopentadiene material, the impact toughness is only 2.19KJ/m2Increased to 3.08KJ/m2。
From the results of comparative example 2, comparative example 1 and comparative example 2, the inventors found that the yield strength, tensile toughness and impact toughness of polydicyclopentadiene composite materials prepared by filling 0.2 parts by mass of silica particles are all improved. However, the modified silica is significantly superior to vinyl silica and ethyl silica with respect to the improvement of impact toughness. Through impact fracture morphology analysis, see fig. 2, the inventors found that pure polydicyclopentadiene had a flat cross section (fig. 2a) and almost no crack propagation, while the addition of vinyl and ethyl silica (fig. 2c, 2d) improved the crack propagation in the cross section, while the addition of modified silica (fig. 2b) gave the best results. Through reaction mechanism analysis, the inventor finds that under the action of a catalyst, vinyl can participate in ring-opening metathesis polymerization of dicyclopentadiene to generate chemical bonding, but the reduction of the crosslinking degree can be caused; the ethyl does not participate in the ring-opening metathesis polymerization of the dicyclopentadiene, and belongs to pure physical strengthening and toughening. The modified silicon dioxide contains ethyl and vinyl, so that after the modified silicon dioxide is added, the excessive reduction of the crosslinking degree caused by the vinyl can be inhibited, and the strong chemical bonding effect can be ensured, so that the modified silicon dioxide is excellent in improvement of yield strength, tensile toughness and impact toughness.
Claims (5)
1. A polydicyclopentadiene composite material is obtained by reacting raw material compositions, and is characterized in that: the raw material composition comprises 100 parts by mass of dicyclopentadiene, 0.01-2 parts by mass of modified silica and 0.01-0.5 part by mass of a catalyst, wherein the modified silica is silica containing ethyl and vinyl, the catalyst is a first-generation Grubbs catalyst or a second-generation Grubbs catalyst, and the total content of the vinyl and the ethyl is 5-20 parts by mass relative to 100 parts by mass of the modified silica.
2. The polydicyclopentadiene composite material of claim 1, wherein the modified silica has an average diameter of 100-1500 nm.
3. The polydicyclopentadiene composite material according to claim 1, wherein the modified silica is contained in an amount of 0.01 to 0.5 part by mass relative to 100 parts by mass of dicyclopentadiene.
4. The method for preparing polydicyclopentadiene composite material according to claim 1, comprising the step (1) and the step (2),
step (1): preparing modified silicon dioxide;
step (2): and (2) uniformly mixing dicyclopentadiene, a catalyst and the modified silicon dioxide obtained in the step (1), and carrying out in-situ polymerization to obtain the polydicyclopentadiene composite material.
5. The method for preparing polydicyclopentadiene composite material according to claim 4, wherein step (1) is carried out by synthesizing modified silica in one step by using a silane coupling agent containing a vinyl group and a silane coupling agent containing an ethyl group by a sol-gel method.
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