CN103951935B - SiO 2-Al 2o 3/ PU-EP matrix material and preparation method - Google Patents
SiO 2-Al 2o 3/ PU-EP matrix material and preparation method Download PDFInfo
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- CN103951935B CN103951935B CN201410084954.5A CN201410084954A CN103951935B CN 103951935 B CN103951935 B CN 103951935B CN 201410084954 A CN201410084954 A CN 201410084954A CN 103951935 B CN103951935 B CN 103951935B
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Abstract
<b>SiO
2-Al
2o
3/ PU-EP</b><bGreat T.GreaT.GT matrix material and preparation method.The shortcoming of the unmodified epoxide resin polymer of </b><bGreatT.Gre aT.GT in performance makes its application be limited to.The present invention includes: (</b><bGreatT.Gre aT.GT1</b><bGrea tT.GreaT.GT) </b><bGreatT.Gre aT.GTAl
2o
3</b><bGreatT.Gre aT.GT and </b><bGreatT.Gre aT.GTSiO
2the modification of </b><bGreatT.Gre aT.GT nanoparticle: with coupling agent </b><bGreatT.Gre aT.GTKH-550</b>< b> to nanometer </b><bGreatT.Gre aT.GTAl
2o
3</b><bGreatT.Gre aT.GT carries out modification, and with coupling agent </b><bGreatT.Gre aT.GTKH-560</b>< b> to nanometer </b><bGreatT.Gre aT.GTSiO
2</b><bGreatT.Gre aT.GT carries out modification, the </b><bGreatT.Gre aT.GTAl of modification
2o
3</b><bGreatT.Gre aT.GT and </b><bGreatT.Gre aT.GTSiO
2</b><bGreatT.Gre aT.GT is as mineral filler; the preparation of (</b><bGreatT.Gre aT.GT2</b><bGrea tT.GreaT.GT) </b><bGreatT.Gre aT.GTPU-EP</b><b > system: adopt epoxy resin </b><bGreatT.Gre aT.GTEP</b><bGre atT.GreaT.GT as reactive matrix, urethane </b><bGreatT.Gre aT.GTPU</b><bGre atT.GreaT.GT is toughner, methyl tetrahydro phthalic anhydride </b><bGreatT.Gre aT.GTMeTHPA</b>< b> is solidifying agent </b><bGreatT.Gre aT.GT, preparation </b><bGreatT.Gre aT.GTPU-EP</b><b > polymkeric substance, (</b><bGreatT.Gre aT.GT3</b><bGrea tT.GreaT.GT) prepares </b><bGreatT.Gre aT.GTSiO
2al
2o
3/ PU-EP</b><bGreat T.GreaT.GT nano composite material: under nanoparticle adds the constant prerequisite of total amount, with the nanometer </b><bGreatT.Gre aT.GTSiO of different ratios
2</b><bGreatT.Gre aT.GT and </b><bGreatT.Gre aT.GTAl
2o
3</b><bGreatT.Gre aT.GT adopts blended method to carry out modification to </b><bGreatT.Gre aT.GTPU-EP</b><b > polymeric matrix, and prepares product of the present invention.</b><bGreatT.Gre aT.GT the present invention is used for </b><bGreatT.Gre aT.GTSiO
2-Al
2o
3the preparation </b><bGreatT.Gre aT.GT of/PU-EP</b><bGreat T.GreaT.GT matrix material.</b>
Description
Technical field:
The present invention relates to a kind of SiO
2-Al
2o
3the preparation method of/PU-EP matrix material.
Background technology:
Because epoxy resin has excellent characteristic, be therefore widely used in the every field of national economy.No matter no matter is high-technology field or field of general technology, be national defense and military industry, or civilian industry, and even can see its trace in daily life.Epoxy resin application formula, the diversity of forming method, handiness are difficult to find in high molecular polymer.For it modification, curing mechanism and product structure, performance research seem more active compared with the research that product synthesizes, achieve larger.But unmodified epoxide resin polymer some shortcoming in performance makes it be limited in the application of a lot of key areas.
The present invention is through the Al of KH-550 modification
2o
3with the SiO of KH-560 modification
2, select two kinds of inorganic components under different ratios, take urethane as toughner, epoxy E-51 is matrix resin, the SiO of preparation viscosity and proper properties
2-Al
2o
3/ PU-EP polymeric matrix.Under the effect of different coupling agents, nanoparticle can be made to be dispersed in PU-EP matrix uniformly, finally reach the object improving nano composite material over-all properties.Use Al
2o
3and SiO
2two kinds of nano materials carry out modification to epoxy resin, utilize the complementarity of the nano material of different shape and often kind of material can carry out the feature of modification to the performance of epoxy resin, its performance can be made to reach comprehensive raising.
Summary of the invention:
The object of this invention is to provide a kind of SiO
2-Al
2o
3/ PU-EP matrix material and preparation method.
Above-mentioned object is realized by following technical scheme:
A kind of SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, the method comprises the steps:
(1) Al
2o
3and SiO
2the modification of nanoparticle: with coupling agent KH-550 to nanometer Al
2o
3carry out modification, and with coupling agent KH-560 to Nano-meter SiO_2
2carry out modification, the Al of modification
2o
3and SiO
2as mineral filler;
(2) preparation of PU-EP system: adopt epoxy resin as reactive matrix, polyurethane PU is toughner, and methyl tetrahydro phthalic anhydride MeTHPA is solidifying agent, preparation PU-EP polymkeric substance;
(3) SiO is prepared
2-Al
2o
3/ PU-EP nano composite material: under nanoparticle adds the constant prerequisite of total amount, with the Nano-meter SiO_2 of different ratios
2and Al
2o
3adopt blended method to change one's profession to PU-EP polymeric matrix, and prepare SiO
2-Al
2o
3/ PU-EP nano composite material;
Described SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, the Al described in step (1)
2o
3and SiO
2the method of the modification of nanoparticle is, with coupling agent KH-550 modified Nano Al
2o
3, get the nanometer Al that 3-5g is fully dry
2o
3with 100-120mL dehydrated alcohol, stirring at normal temperature 30min, gets 0.1-0.2g coupling agent KH-550 and 4-5g distilled water, adds 0.1-0.5mL Glacial acetic acid, and adjust ph, then the KH-550 mixed solution regulating pH value is joined nanometer Al by pH ≈ 3, standing 10min
2o
3mixed solution in, temperature is stir 4h in the thermostat water bath of 80 DEG C, utilizes vacuum filtration pump suction filtration and by washing with alcohol, dry 3h under 60 DEG C of conditions, and it is stand-by to take out grinding, KH-560 modified Nano SiO
2, get the Nano-meter SiO_2 that 4-5g is fully dry
2with 80-100mL dehydrated alcohol, under the condition of 80 DEG C, ultrasonic disperse 0.5h.Get coupling agent KH-560 and the 40-50mL dehydrated alcohol of 0.1-0.5g, temperature is stir 4h in the thermostat water bath of 80 DEG C, and utilize vacuum filtration pump to carry out suction filtration and use washing with alcohol, 80 DEG C of dry 12h, taking-up grinding is stand-by.
Described SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, the method of the preparation of the PU-EP system described in step (2) is, by the epoxy resin E-51 of 10.00g, get 2-4g urethane, by epoxy resin and urethane mixing, temperature is stirring reaction 1h in the thermostat water bath of 80 DEG C, then the temperature of water-bath is dropped to 50 ~ 55 DEG C, add promotor imidazoles 0.01-0.02g afterwards, and add solidifying agent methyl tetrahydro phthalic anhydride 7-9g, acid anhydrides Dosage calculation formula is:
When having promotor to exist in reacting: K=1, the actual amount of acid anhydrides is drawn by the formulae discovery of acid anhydrides consumption, the concrete consumption of Imidizole accelerator is the 0.1-0.2wt% of substrate ring epoxy resins quality, after having added promotor imidazoles and solidifying agent acid anhydrides, Keep agitation reaction 3 ~ 4h, treat that promotor imidazoles dissolves completely in system, the epoxy resin reacted completely and polyurethane mixture are placed in vacuum filter air pump, small bubbles in removing glue, lacquer disk(-sc) inwall being coated releasing agent puts into baking oven preheating, then the glue reacted completely in beaker is evenly poured in lacquer disk(-sc) slowly, make glue smooth be layered on mould, finally the lacquer disk(-sc) completed is put into baking oven and carry out gradient increased temperature solidification, curing process is: 80 DEG C/2h+120 DEG C/1h+150 DEG C/1h+180 DEG C/1h, finally obtained cured article PU-EP.
Described SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, the SiO described in step (1)
2-Al
2o
3the preparation method of/PU-EP nano composite material is, 10.00g epoxy resin and 2-4g urethane is added in 50mL beaker, temperature is stirring reaction 1h in the thermostat water bath of 80 DEG C, after system epoxy resin and urethane mix, by the Al through KH-550 modification
2o
3with the SiO through KH-560 modification
2-add wherein, in the thermostat water bath of 80 DEG C, stirring reaction 1h, treats Nano-meter SiO_2
2-and nanometer Al
2o
3be uniformly dispersed in system, after the temperature of thermostat water bath drops to 50-55 DEG C, solidifying agent methyl tetrahydro phthalic anhydride and promotor imidazoles is added successively respectively again in system, stir about 1.5h, treat that promotor imidazoles dissolves completely in system, the beaker reacted completely is placed in vacuum filter air pump, small bubbles in removing glue, lacquer disk(-sc) inwall being coated releasing agent puts into baking oven preheating, then the glue reacted completely in beaker is evenly poured in lacquer disk(-sc) slowly, make glue smooth be layered on mould, finally the lacquer disk(-sc) completed is put into baking oven and carry out gradient increased temperature solidification, curing process is: 80 DEG C/2h+120 DEG C/1h+150 DEG C/1h+180 DEG C/1h, final curing obtains SiO2-Al2O3/PU-EP cured article.
According to SiO prepared by above method
2--Al
2o
3/ PU-EP matrix material.
Beneficial effect:
1. the present invention is through the nanometer Al of coupling agent KH-550 modification
2o
3, and through the SiO of coupling agent KH-560 modification
2, agglomeration reduces, and the consistency between nanoparticle and matrix is strengthened.
. the present invention works as Nano-meter SiO_2
2doping be 4.5wt%, nanometer Al
2o
3massfraction 5.5wt% time, the effect that nanoparticle disperses in PU-EP matrix is best, and shearing resistance reaches maximum value is 28.5MPa, improves about 23% than the PU-EP system (22.13MPa) of non-doped with nanometer particle.Now disruptive strength also reaches maximum, reaches maximum value 15.0kV/mm.
. specific inductivity of the present invention is along with Nano-meter SiO_2
2with nanometer Al
2o
3the change of ratio and different.Work as Nano-meter SiO_2
2addition increase gradually, nanometer Al
2o
3addition when reducing gradually, the specific inductivity of matrix material increases gradually.Work as Nano-meter SiO_2
2doping be 4.5wt%, nanometer Al
2o
3doping when being 5.5wt%, the dielectric constant values of matrix material reaches maximum, is 4.56.
. heat decomposition temperature of the present invention is along with Nano-meter SiO_2
2with nanometer Al
2o
3the change of ratio and different.Work as Nano-meter SiO_2
2doping be 4.5wt%, nanometer Al
2o
3doping when being 5.5wt%, the heat decomposition temperature of the matrix material front material that comparatively adulterates improves 20 DEG C.
Accompanying drawing illustrates:
Accompanying drawing 1 is syntheti c route schema of the present invention.
Accompanying drawing 2 is coupling agent modified Al
2o
3process flow sheet.
Accompanying drawing 3 is coupling agent modified SiO
2process flow sheet.
Embodiment:
Embodiment 1:
A kind of SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, the method comprises the steps:
(1) Al
2o
3and SiO
2the modification of nanoparticle: with coupling agent KH-550 to nanometer Al
2o
3carry out modification, and with coupling agent KH-560 to Nano-meter SiO_2
2carry out modification, the Al of modification
2o
3and SiO
2as mineral filler;
(2) preparation of PU-EP system: adopt epoxy resin as reactive matrix, polyurethane PU is toughner, and methyl tetrahydro phthalic anhydride MeTHPA is solidifying agent, preparation PU-EP polymkeric substance;
(3) SiO is prepared
2-Al
2o
3/ PU-EP nano composite material: under nanoparticle adds the constant prerequisite of total amount, with the Nano-meter SiO_2 of different ratios
2and Al
2o
3adopt blended method to change one's profession to PU-EP polymeric matrix, and prepare SiO
2-Al
2o
3/ PU-EP nano composite material;
Embodiment 2:
SiO according to embodiment 1
2-Al
2o
3the preparation method of/PU-EP matrix material, the Al described in step (1)
2o
3and SiO
2the method of the modification of nanoparticle is, with coupling agent KH-550 modified Nano Al
2o
3, get the nanometer Al that 3-5g is fully dry
2o
3with 100-120mL dehydrated alcohol, stirring at normal temperature 30min, gets 0.1-0.2g coupling agent KH-550 and 4-5g distilled water, adds 0.1-0.5mL Glacial acetic acid, and adjust ph, then the KH-550 mixed solution regulating pH value is joined nanometer Al by pH ≈ 3, standing 10min
2o
3mixed solution in, temperature is stir 4h in the thermostat water bath of 80 DEG C, utilizes vacuum filtration pump suction filtration and by washing with alcohol, dry 3h under 60 DEG C of conditions, and it is stand-by to take out grinding, KH-560 modified Nano SiO
2, get the Nano-meter SiO_2 that 4-5g is fully dry
2with 80-100mL dehydrated alcohol, under the condition of 80 DEG C, ultrasonic disperse 0.5h.Get coupling agent KH-560 and the 40-50mL dehydrated alcohol of 0.1-0.5g, temperature is stir 4h in the thermostat water bath of 80 DEG C, and utilize vacuum filtration pump to carry out suction filtration and use washing with alcohol, 80 DEG C of dry 12h, taking-up grinding is stand-by.
Embodiment 3:
SiO according to embodiment 1
2-Al
2o
3the preparation method of/PU-EP matrix material, the method of the preparation of the PU-EP system described in step (2) is, by the epoxy resin E-51 of 10.00g, get 2-4g urethane, by epoxy resin and urethane mixing, temperature is stirring reaction 1h in the thermostat water bath of 80 DEG C, then the temperature of water-bath is dropped to 50 ~ 55 DEG C, add promotor imidazoles 0.01-0.02g afterwards, and add solidifying agent methyl tetrahydro phthalic anhydride 7-9g, acid anhydrides Dosage calculation formula is:
When having promotor to exist in reacting: K=1, the actual amount of acid anhydrides is drawn by the formulae discovery of acid anhydrides consumption, the concrete consumption of Imidizole accelerator is the 0.1-0.2wt% of substrate ring epoxy resins quality, after having added promotor imidazoles and solidifying agent acid anhydrides, Keep agitation reaction 3 ~ 4h, treat that promotor imidazoles dissolves completely in system, the epoxy resin reacted completely and polyurethane mixture are placed in vacuum filter air pump, small bubbles in removing glue, lacquer disk(-sc) inwall being coated releasing agent puts into baking oven preheating, then the glue reacted completely in beaker is evenly poured in lacquer disk(-sc) slowly, make glue smooth be layered on mould, finally the lacquer disk(-sc) completed is put into baking oven and carry out gradient increased temperature solidification, curing process is: 80 DEG C/2h+120 DEG C/1h+150 DEG C/1h+180 DEG C/1h, finally obtained cured article PU-EP.
Embodiment 4:
SiO according to embodiment 1
2-Al
2o
3the preparation method of/PU-EP matrix material, the SiO described in step (1)
2-Al
2o
3the preparation method of/PU-EP nano composite material is, 10.00g epoxy resin and 2-4g urethane is added in 50mL beaker, temperature is stirring reaction 1h in the thermostat water bath of 80 DEG C, after system epoxy resin and urethane mix, by the Al through KH-550 modification
2o
3with the SiO through KH-560 modification
2-add wherein, in the thermostat water bath of 80 DEG C, stirring reaction 1h, treats Nano-meter SiO_2
2-and nanometer Al
2o
3be uniformly dispersed in system, after the temperature of thermostat water bath drops to 50-55 DEG C, solidifying agent methyl tetrahydro phthalic anhydride and promotor imidazoles is added successively respectively again in system, stir about 1.5h, treat that promotor imidazoles dissolves completely in system, the beaker reacted completely is placed in vacuum filter air pump, small bubbles in removing glue, lacquer disk(-sc) inwall being coated releasing agent puts into baking oven preheating, then the glue reacted completely in beaker is evenly poured in lacquer disk(-sc) slowly, make glue smooth be layered on mould, finally the lacquer disk(-sc) completed is put into baking oven and carry out gradient increased temperature solidification, curing process is: 80 DEG C/2h+120 DEG C/1h+150 DEG C/1h+180 DEG C/1h, final curing obtains SiO2-Al2O3/PU-EP cured article.
Embodiment 5:
SiO prepared by the method according to case study on implementation 1 or 2 or 3 or 4
2--Al
2o
3/ PU-EP matrix material.
Claims (1)
1. a SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, is characterized in that: the method comprises the steps:
With coupling agent KH-550 modified Nano Al
2o
3, get the nanometer Al that 3-5g is fully dry
2o
3with 100-120mL dehydrated alcohol, stirring at normal temperature 30min, gets 0.1-0.2g coupling agent KH-550 and 4-5g distilled water, adds 0.1-0.5mL Glacial acetic acid, and adjust ph, then the KH-550 mixed solution regulating pH value is joined nanometer Al by pH=3, standing 10min
2o
3mixed solution in, temperature is stir 4h in the thermostat water bath of 80 DEG C, utilizes vacuum filtration pump suction filtration and by washing with alcohol, dry 3h under 60 DEG C of conditions, and it is stand-by to take out grinding, KH-560 modified Nano SiO
2, get the Nano-meter SiO_2 that 4-5g is fully dry
2with 80-100mL dehydrated alcohol, under the condition of 80 DEG C, ultrasonic disperse 0.5h, get coupling agent KH-560 and the 40-50mL dehydrated alcohol of 0.1-0.5g, temperature is stir 4h in the thermostat water bath of 80 DEG C, utilize vacuum filtration pump to carry out suction filtration and use washing with alcohol, 80 DEG C of dry 12h, taking-up grinding is stand-by;
In 50mL beaker, add 10.00g epoxy resin and 2-4g urethane, temperature is stirring reaction 1h in the thermostat water bath of 80 DEG C, after system epoxy resin and urethane mix, by the Al through KH-550 modification
2o
3with the SiO through KH-560 modification
2add wherein, in the thermostat water bath of 80 DEG C, stirring reaction 1h, treats Nano-meter SiO_2
2with nanometer Al
2o
3be uniformly dispersed in system, after the temperature of thermostat water bath drops to 50-55 DEG C, solidifying agent methyl tetrahydro phthalic anhydride and promotor imidazoles is added successively respectively again in system, stir 1.5h, treat that promotor imidazoles dissolves completely in system, the beaker reacted completely is placed in vacuum filter air pump, small bubbles in removing glue, lacquer disk(-sc) inwall being coated releasing agent puts into baking oven preheating, then the glue reacted completely in beaker is evenly poured in lacquer disk(-sc) slowly, make glue smooth be layered on mould, finally the lacquer disk(-sc) completed is put into baking oven and carry out gradient increased temperature solidification, curing process is: 80 DEG C/2h+120 DEG C/1h+150 DEG C/1h+180 DEG C/1h, final curing obtains SiO
2-Al
2o
3/ PU-EP cured article.
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CN104262906B (en) * | 2014-09-26 | 2016-08-24 | 西安理工大学 | Nano filling works in coordination with filling epoxy resin composite coating and its preparation method and application |
CN108709861A (en) * | 2018-06-01 | 2018-10-26 | 廊坊立邦涂料有限公司 | A kind of detection method of resin miscible |
CN111234507A (en) * | 2020-03-23 | 2020-06-05 | 扬州工业职业技术学院 | Preparation method of TiO2PU composite material |
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