CN105038128A - Vi-POSS-ZnO/EP anti-UV toughened composite material and preparation method thereof - Google Patents
Vi-POSS-ZnO/EP anti-UV toughened composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Vi-POSS-ZnO/EP anti-UV toughened composite material and a preparation method thereof. The composite material is composed of the following raw materials in parts by weight: 100 parts of epoxy resin, 0.1 to 3 parts of modified nano zinc oxide, 0.1 to 10 parts of octavinyl silsesquioxane, and 3 parts of 2-ethyl-4-methylimidazole. The epoxy resin is taken as the matrix, modified nano zinc oxide is taken as the modifier, octavinyl silsesquioxane is used as the toughening agent, and 2-ethyl-4-methylimidazole is taken as the curing agent. Octavinyl silsesquioxane is used as the toughening agent and is added into the epoxy resin matrix, the toughness of the composite material can be effectively improved; the modified nano zinc oxide can effectively improve the anti-UV-ageing performance of the composite material, and the composite material has the advantages of good anti-UV-aging property, strong impact resistant performance, simple preparation technology, and cheap raw materials, and can be applied to industrial production.
Description
Technical field
The present invention relates to the preparing technical field of matrix material, be specifically related to a kind of Vi-POSS-ZnO/EP uvioresistant toughening composition and preparation method thereof.
Background technology
Epoxy resin (EP) is most widely used a kind of thermosetting resin in polymer composites, due to features such as its good mechanical property, thermotolerance, high-adhesiveness and insulativity, be used widely in fields such as material of construction, electric material, sizing agent and advanced composite materials.Because cross-linking density is large after EP solidification, there is the shortcomings such as matter is crisp, shock-resistance, make it apply and be restricted; Simultaneously, some EP matrix material needs long-term exposure under sunlight and UV-light, such as, as the bisphenol A type epoxy resin of general-purpose diode packaged material, particularly based on white light LEDs (UV-WLED) diode of UV-light, then need to possess higher absorption of UV, prevent ultraviolet from revealing, require that EP resin itself possesses good anti-ultraviolet ageing ability.Therefore, about the modification problem of epoxy resin, always be the problem that Chinese scholars is paid close attention to.
In recent years, some nanoparticles effectively can improve the toughness of matrix material, thermostability and anti-ultraviolet ageing ability, the focus making these particles become investigators to pay close attention to, modification is carried out to traditional epoxy resin and prepares uvioresistant toughening composition with the technical requirements used under meeting high intensity ultraviolet radiation, further raising product work-ing life, oneself becomes the developing direction of epoxide resin type special composite material.
Summary of the invention
The object of the present invention is to provide a kind of Vi-POSS-ZnO/EP uvioresistant toughening composition and preparation method thereof, it passes through modified nano zine oxide as properties-correcting agent, using eight vinyl silsesquioxanes as toughner, the matrix material that Controlling Technology parameter prepares has the advantages such as the mechanical propertys such as anti-ultraviolet ageing ability is good, shock resistance are strong.
One of task of the present invention is to provide a kind of Vi-POSS-ZnO/EP uvioresistant toughening composition.
A kind of Vi-POSS-ZnO/EP uvioresistant toughening composition, according to parts by weight, it is prepared from primarily of following raw material: the eight vinyl silsesquioxanes of the epoxy resin of 100 parts, the modified nano zinc oxide of 0.1-3 part, 0.1-10 part and 2-ethyl-4 Methylimidazole of 3 parts; Wherein, epoxy resin is as matrix, and modified nano zinc oxide is as properties-correcting agent, and eight vinyl silsesquioxanes are as toughner, and 2-ethyl-4 Methylimidazole is as solidifying agent.
The Advantageous Effects that technique scheme is directly brought is:
Join in epoxy resin-base using eight vinyl silsesquioxanes as toughner, effectively can improve the toughness of matrix material, modified nano zinc oxide effectively can improve the anti-ultraviolet ageing ability of matrix material, it is good that above-mentioned raw materials combines the matrix material resistance to UV aging prepared, and shock resistance mechanical property is strong.
As a preferred version of the present invention, the parts by weight of described raw material are: the eight vinyl silsesquioxanes of the epoxy resin of 100 parts, the modified nano zinc oxide of 0.5-3 part, 1-8 part and 2-ethyl-4 Methylimidazole of 3 parts.
The effect adding eight vinyl silsesquioxanes is: polyhedral silsesquioxane (POSS), it is the hybrid inorganic-organic materials that a class has nano-scale, the chemical structure of its uniqueness, as (1) cage modle framework, the nanostructure of POSS itself possesses extraordinary symmetry, and overall cage modle skeleton construction makes it have good dielectricity and optical property; Simultaneously in increase toughness of material, POSS nanoparticle can stop further expanding of tiny crack tip, and can cause crazing or shear zone or molecular chain and rearrange; (2) inorganic kernel, the inorganic kernel of the silica skeleton composition that Si-O alternately connects, can suppress the chain movement of polymer molecule, thus make hybrid material show good thermostability, mechanical property and flame retardant resistance; (3) nano-scale, the three-dimensional dimension of POSS is between 1.3nm, distance wherein between Si-Si atom is 0.5nm, the spacing of R-R group is 1.5nm, is typical nano material, thus possesses the small-size effect of nanoparticle, surface and interface effect, quantum size effect, macro quanta tunnel effect etc., thus possess stronger over-all properties; (4) R base diversity, POSS application in the polymer depends primarily on R base, R base can be reactive group, as thiazolinyl, epoxy group(ing), amino etc., can come, between polymkeric substance, grafting or polyreaction occur by reactive R base, thus produce chemical bonding effect between polymkeric substance, introduce POSS base, what realize on molecular layer is dispersed, improves polymer performance; When R base is inertia group, as alkyl, alkylene, aryl etc., the consistency between POSS nanostructure and polymkeric substance can be regulated.
The effect adding modified ZnO particle is: ZnO particle belongs to N-type semiconductor, its energy gap is 32eV, when nano zine oxide is when being subject to uviolizing, electronics Absorbable rod ultraviolet in valence band and be excited on conduction band, produce hole-electron pair simultaneously, have and absorb ultraviolet function, thus improve the anti-ultraviolet ageing ability of matrix material, and as ZnO Nanoparticles, can well with organism epoxy resin-base Homogeneous phase mixing, by ZnO is carried out pre-treatment can improve well ZnO dispersion effect effect.
As another preferred version of the present invention, the parts by weight of described raw material are: the epoxy resin of 100 parts, the modified nano zinc oxide of 2 parts, the eight vinyl silsesquioxanes of 6 parts and 2-ethyl-4 Methylimidazole of 3 parts.
Two of task of the present invention is to provide the preparation method of above-mentioned matrix material.
The preparation method of above-mentioned Vi-POSS-ZnO/EP uvioresistant toughening composition, comprises the following steps successively:
The preparation of step a, properties-correcting agent, is scattered in nanoparticle ZnO in triethylamine alcohol solution, adds the aqueous ethanolic solution containing silane coupling agent under high-speed stirring under ultrasonication, regulates pH value to be neutral, is placed in planetary ball mill ball milling 60mins;
By the ZnO after ball milling, with centrifugation under room temperature after isopropanol, circulate three times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, obtains modified nano zine oxide;
The preparation of step b, epoxy resin-base, takes a certain amount of epoxy resin and is positioned over preheating in baking oven, takes out and is placed in the water bath containers of 80 DEG C, for subsequent use;
Step c, ultrasonic blended treatment step, by nano zine oxide modified for step a gained and the mixing of step b gained epoxy resin-base, add eight vinyl silsesquioxanes and 2-ethyl-4 Methylimidazole more successively, obtain biased sample, described biased sample is positioned in water bath containers and stirs, to be mixed evenly after put into setting the vacuum drying oven of pressure under-0.1MPa in deaeration process 1h, obtain the sample after deaeration process;
Steps d, by the samples pre-heated after step c deaeration process, pour in Teflon mould after viscosity reduces, putting into temperature is that the baking oven of 100 DEG C solidifies 1h, and by the matrix material demoulding after solidification, namely grinding process obtains product.
Preferably, in step a, with 16000rpm centrifugation 60mins under room temperature after isopropanol.
Preferably, in step b, the temperature of baking oven is set as 100 DEG C, preheating 10mins.
Preferably, in step c, described biased sample is positioned in the water-bath magnetic agitation pot of 80 DEG C.
Preferably, in steps d, the sample after deaeration process to be placed in the baking oven of 80 DEG C preheating 3 minutes.
The Advantageous Effects that the present invention brings:
Choosing at raw material, present invention utilizes Vi-POSS and ZnO inorganic nano-particle and modification is carried out to epoxy resin, widen the range of application of epoxy-resin systems as sizing agent, by improve toughness and the anti-ultraviolet ageing ability of modified composite material, making it not only can be widely used in the electronic package material fields such as LED and can also be applied to the advanced composite material fields such as aerospace; And this composite material preparation process is simple, and cheaper starting materials, is conducive to realizing suitability for industrialized production.
In cost budgeting, the price of silane coupling agent KH-560, solidifying agent trolamine and epoxy resin is lower, itself is also well positioned to meet the performance of product simultaneously, can reduces costs.
In preparation method, one, the present invention is to the surface modification of nano zine oxide, to be scattered in triethylamine alcohol solution under ultrasonication by chemical method, the processing modes such as the aqueous ethanolic solution containing silane coupling agent are added under high-speed stirring, obtain modified nano zine oxide, by chemical method, surface treatment is carried out to nano zine oxide, efficiently solve the reuniting effect of nanoparticle in dispersion process, make it be dispersed in uniformly in epoxy resin-base, greatly enhance the resistance to UV aging of product; They are two years old, have employed ultrasonic blended and prepolymer is carried out deaeration process under-0.1MPa when matrix material synthesizes, obtain the toughening composition of mechanical property excellence, by the sample that this ultrasonic blending method obtains, after crosslinking curing, internal structure is tightr, without micro-shape bubble, solve because interior tissue pore is on the impact of material property, improve the toughness of product.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention will be further described:
Fig. 1 is the test result graphic representation that the massfraction of material oxidation zinc affects ultraviolet absorption value;
Fig. 2 is the matrix material X-ray diffraction test curve that the present invention prepares;
Fig. 3 is that the massfraction of raw material Vi-POSS affects test result graphic representation to product flexural strength;
Fig. 4 is that the massfraction of raw material Vi-POSS affects test result graphic representation to product shock strength;
The scanning electron microscopic picture that the fracture micro-appearance that Fig. 5 (a) is matrix material of the present invention (the EP epoxy resin without Vi-POSS/ZnO modification) is analyzed;
Fig. 5 (b) is the scanning electron microscopic picture of the end Morphology analysis of matrix material of the present invention (through the EP epoxy resin that Vi-POSS/ZnO is modified);
The scanning electron microscopic picture that the fracture micro-appearance that Fig. 5 (c) is matrix material of the present invention (without the EP epoxy resin of Vi-POSS/ZnO modification after ultraviolet radiation) is analyzed;
Fig. 5 (d) is the scanning electron microscopic picture of the end Morphology analysis of matrix material of the present invention (through the EP epoxy resin of Vi-POSS/ZnO modification after ultraviolet radiation).
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further details.
Following explanation is done to part material selected by the present invention below:
KH560: chemical name is γ-glycidyl ether oxygen propyl trimethoxy silicane, molecular formula is CH
2-CHCH
2-O (CH
2)
3si (OCH
3)
3;
Vi-POSS: chemical name is eight vinyl silsesquioxanes, and molecular formula is C
16h
24o
12sI
8;
EMI: chemical name is 2-ethyl-4 Methylimidazole, and structural formula is C
6h
10n
2;
The above-mentioned raw material do not explained also is bought by commercial channel and is obtained.
Concrete preparation method below in conjunction with embodiment 1-embodiment 8 pairs of matrix materials of the present invention elaborates.
Embodiment 1:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:0.5:6, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 2:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:1:6, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 3:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:2:6, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 4:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:3:6, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h, the matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 5:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:2:2, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 6:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:2:4, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 7:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:2:6, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
Embodiment 8:
The preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition of the present invention, specifically comprises the following steps:
Step 1, ZnO Nanoparticles to be scattered in triethylamine alcohol solution under ultrasonication, under high-speed stirring, to add the aqueous ethanolic solution containing KH-560, regulate pH value be neutrality, be placed in planetary ball mill ball milling 60mins;
Step 2, by the ZnO after ball milling obtained above, with 16000rpm centrifugation 60mins under room temperature after isopropanol, circulate 3 times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, the nanometer ZnO powder of the surface modification obtained is for subsequent use;
Step 3, by massfraction, take 100 parts of epoxy resin, be put in the beaker of 50ML, be placed in 100 DEG C of baking oven preheatings and take out after 10 minutes, be put in 80 DEG C of water-bath magnetic agitation pots;
Step 4, by massfraction, using the epoxy resin after thermal pretreatment as matrix, with modified nano-ZnO, toughner Vi-POSS, mix in the ratio of mass fraction 100:2:8, add 3 parts of solidifying agent 2-ethyls-4 Methylimidazole (EMI) simultaneously;
Step 5, by mixed sample after 80 DEG C of water-bath magnetic agitation 30mins, the condition mixture stirred being put into setting is deaeration process 1h in the vacuum drying oven under normal temperature ,-0.1MPa; After deaeration terminates, take out and to be put in 80 DEG C of baking ovens preheating 3 minutes, pour in Teflon mould after viscosity reduces, put into 100 DEG C of baking ovens after die-filling and solidify 1h; The matrix material demoulding after finally solidifying, and with sand paper, coarse place is polished smooth, obtain finished product matrix material.
For understanding the present invention better, existing the present invention is described in detail by reference to the accompanying drawings.
The test result graphic representation that the massfraction of the matrix material zinc oxide of Fig. 1 prepared by embodiment 1-8 affects ultraviolet absorption value; The matrix material X-ray diffraction test curve of Fig. 2 prepared by embodiment 1-8; The massfraction of the matrix material Vi-POSS of Fig. 3 prepared by embodiment 1-8 affects test result graphic representation to product flexural strength; The massfraction of the matrix material Vi-POSS of Fig. 4 prepared by embodiment 1-8 affects test result graphic representation to product shock strength; The scanning electron microscopic picture of the fracture micro-appearance analysis of Fig. 5 (a), Fig. 5 (b), Fig. 5 (c), Fig. 5 (d) matrix material prepared by embodiment 1-8.
As shown in Figure 1, along with the increase of ZnO addition, ultraviolet absorption degree first increases and then decreases, when addition is 2% time, ultraviolet absorption effect is best, when ZnO content increase further to 3% time, rate of absorbing UV reduces on the contrary, the reason reduced may be being on the increase along with nano level ZnO, and the agglomeration of nano particle is more obvious, affects dispersion effect.
At UV-light UVB (280-190nm), UVC (315-280nm) wave band, cause epoxy resin ultraviolet ageing main region, known by test result, the anti-ultraviolet ageing ability that modified nano-ZnO mixes improving epoxy resin improves significantly.
As shown in Figure 2, the X-ray peak intensity of pure organism epoxy resin is almost 0, and inorganics Vi-POSS and ZnO belongs to crystalline structure.Composed from XRD figure, Vi-POSS to add after EP when 2 θ are 18-20, there is stronger absorption peak, by blending method, Vi-POSS and ZnO is added in EP simultaneously, only there is stronger absorption peak when 2 θ are 18-20 in same, Vi-POSS and ZnO uniform and epoxy resin mixing is after blending described.
As shown in Figure 3, before uv-radiation, along with the increase of Vi-POSS addition, flexural strength presents the trend of first increases and then decreases, and the composite material exhibits after corresponding uv-radiation goes out same performance.When Vi-POSS content is increased to 6wt%, the flexural strength of the EP matrix material before and after uv-radiation reaches optimum value.For the sample without UV radiotreatment, the modified matrix material flexural strength of Vi-POSS improves 14.75%; After UV radiation, corresponding flexural strength improves 37.93% respectively, thus confirms the mechanical strength reinforcing effect of POSS.
Along with the further increase of Vi-POSS addition, modified matrix material flexural strength decreases, think, POSS particle and the epoxy resin of hybrid inorganic-organic well can be combined and the cross-linking density of cured article can be made to increase, improve the toughness of material, but add-on is excessive, the uneven easy reunion of the dispersion of POSS particle in resin matrix, thus the bending property of EP matrix material is reduced.
As shown in Figure 4, and the Analysis On Bending Strength result of figure tri-similar.Before uv-radiation, along with the increase of Vi-POSS addition, shock strength presents the trend of first increases and then decreases, and the composite material exhibits after corresponding uv-radiation goes out same performance.When Vi-POSS content is increased to 6wt%, the flexural strength of the EP matrix material before and after uv-radiation reaches optimum value.For the sample without UV radiotreatment, composite impact strength enhancing that Vi-POSS is modified 29.5%; After UV radiation, corresponding shock strength improves 31.19% respectively, thus confirms the mechanical strength reinforcing effect of POSS.
Along with the further increase of Vi-POSS addition, modified composite impact intensity decreases, think, POSS particle and the epoxy resin of hybrid inorganic-organic well can be combined and the cross-linking density of cured article can be made to increase, improve the toughness of material, but add-on is excessive, the uneven easy reunion of the dispersion of POSS particle in resin matrix, thus the impact property of EP matrix material is reduced.
As shown in Fig. 5 (a), before uv-radiation, without EP epoxy resin obvious river shape cleavage shape when the microscopic appearance at rock-candy structure place of Vi-POSS/ZnO modification, be shown to be this matrix material and there is a kind of typical hard brittle material feature.Dimple structure has been there is in Fig. 5 (b) through modified EP epoxy resin section part, this shows that the Vi-POSS/ZnO nanoparticle added changes the inside composition structure of material, the diffusion of the crackle that the dimple structure simultaneously formed produces under can effectively preventing shock action, thus improve the toughness of matrix material.After ultraviolet radiation, unmodified EP surface tissue is as Fig. 5 (c), and than more level and smooth before radiation, Brittleness is more obvious, show that UV-light can reduce EP matrix material breaking strength, and Fig. 5 (d) does not almost change in uv-radiation rear surface structure.And this matrix material mechanical strength test result under ultraviolet radiation modified with the interpolation Vi-POSS analyzed above is consistent, therefore, further demonstrate that the interpolation of Vi-POSS/ZnO nanoparticle can improve the anti-ultraviolet ageing ability of EP matrix material, further improve the physical strength of matrix material simultaneously.
Should be understood that; the above-mentioned description for preferred embodiment is comparatively detailed; therefore the restriction to scope of patent protection of the present invention can not be thought; those of ordinary skill in the art is under enlightenment of the present invention; do not departing under the ambit that the claims in the present invention protect; can also make the various deformation such as replacement, simple combination, request protection domain of the present invention should be as the criterion with claims.
Claims (8)
1. a Vi-POSS-ZnO/EP uvioresistant toughening composition, is characterized in that: according to parts by weight, it is prepared from primarily of following raw material:
The eight vinyl silsesquioxanes of the epoxy resin of 100 parts, the modified nano zinc oxide of 0.1-3 part, 0.1-10 part and 2-ethyl-4 Methylimidazole of 3 parts; Wherein, epoxy resin is as matrix, and modified nano zinc oxide is as properties-correcting agent, and eight vinyl silsesquioxanes are as toughner, and 2-ethyl-4 Methylimidazole is as solidifying agent.
2. Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 1, is characterized in that: the parts by weight of described raw material are: the eight vinyl silsesquioxanes of the epoxy resin of 100 parts, the modified nano zinc oxide of 0.5-3 part, 1-8 part and 2-ethyl-4 Methylimidazole of 3 parts.
3. Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 2, is characterized in that: the parts by weight of described raw material are: the epoxy resin of 100 parts, the modified nano zinc oxide of 2 parts, the eight vinyl silsesquioxanes of 6 parts and 2-ethyl-4 Methylimidazole of 3 parts.
4. the preparation method of the Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 1 or 2 or 3, is characterized in that: comprise the following steps successively:
The preparation of step a, properties-correcting agent, is scattered in nanoparticle ZnO in triethylamine alcohol solution, adds the aqueous ethanolic solution containing silane coupling agent under high-speed stirring under ultrasonication, regulates pH value to be neutral, is placed in planetary ball mill ball milling 60mins; By the ZnO after ball milling, with centrifugation under room temperature after isopropanol, circulate three times, finally the solid sample that centrifugation obtains is put in dry 8h in the vacuum drying oven of 100 DEG C, obtains modified nano zine oxide;
The preparation of step b, epoxy resin-base, takes a certain amount of epoxy resin and is positioned over preheating in baking oven, takes out and is placed in the water bath containers of 80 DEG C, for subsequent use;
Step c, ultrasonic blended treatment step, by nano zine oxide modified for step a gained and the mixing of step b gained epoxy resin-base, add eight vinyl silsesquioxanes and 2-ethyl-4 Methylimidazole more successively, obtain biased sample, described biased sample is positioned in water bath containers and stirs, to be mixed evenly after put into setting the vacuum drying oven of pressure under-0.1MPa in deaeration process 1h, obtain the sample after deaeration process;
Steps d, by the samples pre-heated after step c deaeration process, pour in Teflon mould after viscosity reduces, putting into temperature is that the baking oven of 100 DEG C solidifies 1h, and by the matrix material demoulding after solidification, namely grinding process obtains product.
5. the preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 4, is characterized in that: in step a, with 16000rpm centrifugation 60mins under room temperature after isopropanol.
6. the preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 4, is characterized in that: in step b, and the temperature of baking oven is set as 100 DEG C, preheating 10mins.
7. the preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 4, is characterized in that: in step c, is positioned over by described biased sample in the water-bath magnetic agitation pot of 80 DEG C.
8. the preparation method of Vi-POSS-ZnO/EP uvioresistant toughening composition according to claim 4, is characterized in that: in steps d, and the sample after deaeration process to be placed in the baking oven of 80 DEG C preheating 3 minutes.
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| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
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| CN101985513A (en) * | 2010-05-20 | 2011-03-16 | 复旦大学 | POSS/epoxy nanometer hybrid material and preparation method and application thereof |
| CN103146329A (en) * | 2011-12-07 | 2013-06-12 | 南京工程学院 | Preparation method for epoxy adhesive modified by surface-modified nanoparticles |
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| CN101985513A (en) * | 2010-05-20 | 2011-03-16 | 复旦大学 | POSS/epoxy nanometer hybrid material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
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