CN103951935A - SiO2-Al2O3/PU(polyurethane)-EP(epoxy resin) composite material and preparation method thereof - Google Patents
SiO2-Al2O3/PU(polyurethane)-EP(epoxy resin) composite material and preparation method thereof Download PDFInfo
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- CN103951935A CN103951935A CN201410084954.5A CN201410084954A CN103951935A CN 103951935 A CN103951935 A CN 103951935A CN 201410084954 A CN201410084954 A CN 201410084954A CN 103951935 A CN103951935 A CN 103951935A
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Abstract
The invention discloses a SiO2-Al2O3/PU(polyurethane)-EP(epoxy resin) composite material and a preparation method thereof. Unmodified epoxy resin polymers are limited in application due to shortcomings thereof in the performance. The preparation method of the composite material is as follows: (1) modification of Al2O3 and SiO2 nanoparticles, to be more specific, nano Al2O3 is modified by use of coupling agent KH-550, the nano SiO2 is modified by use of coupling agent KH-560, and the modified Al2O3 and SiO2 are used as inorganic fillers; (2) preparation of a PU-EP system, to be more specific, epoxy resin EP is used as a reaction matrix, PU polyurethane is used as a toughening agent, methyl tetrahydrophthalic anhydride MeTHPA is used as a curing agent for preparation of a PU-EP polymer; (3) preparation of a SiO2Al2O3/PU-EP composite nano material, to be more specific, in the condition of no change on the total adding amount of nanoparticles, nano SiO2 and Al2O3 with different proportions are used for modification of the PU-EP polymer matrix by use of a mixing method, and then the SiO2-Al2O3/PU(polyurethane)-EP(epoxy resin) composite material is obtained. The preparation method is used for the preparation of the SiO2-Al2O3/PU-EP composite material.
Description
technical field:
the present invention relates to a kind of SiO
2
-Al
2
o
3
the preparation method of/PU-EP matrix material.
background technology:
because epoxy resin has good characteristic, therefore in the every field of national economy, be widely used.No matter no matter is high-technology field or current techique field, 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, compared with product, synthetic research seems more active in the research of performance, achieves larger.But unmodified epoxide resin polymer some shortcoming in performance is limited to its application at a lot of key areas.
the present invention is through the Al of KH-550 modification
2
o
3
siO with KH-560 modification
2
, select two kinds of inorganic components under different ratios, take urethane as toughner, epoxy E-51 is matrix resin, preparation viscosity and the suitable SiO of performance
2
-Al
2
o
3
/ PU-EP polymeric matrix.Under the effect of different coupling agents, can make nanoparticle be dispersed in uniformly in PU-EP matrix, finally reach the object that improves nano composite material over-all properties.Use Al
2
o
3
and SiO
2
two kinds of nano materials are carried out modification to epoxy resin, utilize complementarity and every kind of material of the nano material of different shape to the performance of epoxy resin, to carry out the feature of modification, can make its performance reach comprehensive raising.
summary of the invention:
the object of this invention is to provide a kind of SiO
2
-Al
2
o
3
/ PU-EP matrix material and preparation method.
above-mentioned object realizes by following technical scheme:
a kind of SiO
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the method comprises the steps:
(1) Al
2
o
3
and SiO
2
the modification of nanoparticle: use coupling agent KH-550 to nanometer Al
2
o
3
carry out modification, and with coupling agent KH-560 to nanometer SiO
2
carry out modification, the Al of modification
2
o
3
and SiO
2
as 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) prepare SiO
2
-Al
2
o
3
/ PU-EP nano composite material: add under the constant prerequisite of total amount at nanoparticle, with the nanometer SiO of different ratios
2
and Al
2
o
3
adopt the method for blend to change one's profession to PU-EP polymeric matrix, and prepare SiO
2
-Al
2
o
3
/ PU-EP nano composite material;
described SiO
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the Al that step (1) is described
2
o
3
and SiO
2
the method of the modification of nanoparticle is, with coupling agent KH-550 modified Nano Al
2
o
3
, get the nanometer Al that 3-5g is fully dry
2
o
3
with 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 regulates pH value, pH ≈ 3, and then standing 10min joins nanometer Al by the KH-550 mixed solution that regulates pH value
2
o
3
mixed solution in, temperature is to stir 4h in the thermostat water bath of 80 ℃, utilizes vacuum filtration pump suction filtration and by washing with alcohol, dry 3h under 60 ℃ of conditions, take out grind stand-by, KH-560 modified Nano SiO
2
, get the nanometer SiO that 4-5g is fully dry
2
with 80-100mL dehydrated alcohol, under the condition of 80 ℃, ultrasonic dispersion 0.5h.Get coupling agent KH-560 and the 40-50mL dehydrated alcohol of 0.1-0.5g, temperature is to stir 4h in the thermostat water bath of 80 ℃, utilizes vacuum filtration pump to carry out suction filtration and by washing with alcohol, 80 ℃ of dry 12h, take out grind stand-by.
described SiO
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the method of the preparation of the PU-EP system that step (2) is described is, by the epoxy resin E-51 of 10.00 g, get 2-4g urethane, epoxy resin and urethane are mixed, temperature is stirring reaction 1 h in the thermostat water bath of 80 ℃, then the temperature of water-bath is dropped to 50 ~ 55 ℃, add afterwards promotor imidazoles 0.01-0.02 g, and add solidifying agent methyl tetrahydro phthalic anhydride 7-9g, acid anhydrides consumption calculation formula is:
while having promotor to exist in reaction: K=1, by the formula of acid anhydrides consumption, calculate the actual amount of acid anhydrides, the concrete consumption of imidazoles promotor is the 0.1-0.2wt% of substrate ring epoxy resins quality, added after promotor imidazoles and solidifying agent acid anhydrides, continue stirring reaction 3 ~ 4 h, treat that promotor imidazoles dissolves completely in system, the epoxy resin reacting completely and polyurethane mixture are placed in vacuum filter air pump, remove the small bubbles in glue, the lacquer disk(-sc) that inwall is coated to releasing agent is put into baking oven preheating, then the glue reacting completely in beaker is evenly poured in lacquer disk(-sc) slowly, make smooth being layered on mould of glue, finally the lacquer disk(-sc) of completing being put into baking oven carries out gradient increased temperature and solidifies, curing process is: 80 ℃/2 h+120 ℃/1 h+150 ℃/1 h+180 ℃/1 h, finally make cured article PU-EP.
described SiO
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the SiO that step (1) is described
2
-Al
2
o
3
the preparation method of/PU-EP nano composite material is, in 50 mL beakers, add 10.00 g epoxy resin and 2-4g urethane, temperature is stirring reaction 1 h in the thermostat water bath of 80 ℃, after in system, epoxy resin and urethane mix, by the Al through KH-550 modification
2
o
3
with the SiO through KH-560 modification
2
-add wherein, in the thermostat water bath of 80 ℃, stirring reaction 1 h, treats nanometer SiO
2
-and nanometer Al
2
o
3
in system, be uniformly dispersed, the temperature of thermostat water bath drops to after 50-55 ℃, in system, add successively respectively solidifying agent methyl tetrahydro phthalic anhydride and promotor imidazoles again, stir about 1.5 h, treat that promotor imidazoles dissolves completely in system, the beaker reacting completely is placed in vacuum filter air pump, remove the small bubbles in glue, the lacquer disk(-sc) that inwall is coated to releasing agent is put into baking oven preheating, then the glue reacting completely in beaker is evenly poured in lacquer disk(-sc) slowly, make smooth being layered on mould of glue, finally the lacquer disk(-sc) of completing being put into baking oven carries out gradient increased temperature and solidifies, curing process is: 80 ℃/2 h+120 ℃/1 h+150 ℃/1 h+180 ℃/1 h, final curing obtains SiO2-Al2O3/PU-EP cured article.
the SiO preparing according to above method
2
--Al
2
o
3
/ PU-EP matrix material.
beneficial effect:
1. the present invention is through the nanometer Al of coupling agent KH-550 modification
2
o
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 is as nanometer SiO
2
doping be 4.5wt%, nanometer Al
2
o
3
massfraction 5.5wt% time, the effect that nanoparticle disperses in PU-EP matrix is best, and shearing resistance to reach maximum value be 28.5MPa, than the PU-EP system (22.13MPa) of doped with nanometer particle not, improved approximately 23%.Now disruptive strength also reaches maximum, reaches maximum value 15.0 kV/mm.
. specific inductivity of the present invention is along with nanometer SiO
2
with nanometer Al
2
o
3
the variation of ratio and different.As nanometer SiO
2
addition increase gradually, nanometer Al
2
o
3
addition while reducing gradually, the specific inductivity of matrix material increases gradually.As nanometer SiO
2
doping be 4.5wt%, nanometer Al
2
o
3
doping while being 5.5wt%, it is maximum that the dielectric constant values of matrix material reaches, and is 4.56.
. heat decomposition temperature of the present invention is along with nanometer SiO
2
with nanometer Al
2
o
3
the variation of ratio and different.As nanometer SiO
2
doping be 4.5wt%, nanometer Al
2
o
3
doping while being 5.5wt%, before the heat decomposition temperature of matrix material adulterates, material has improved 20 ℃.
accompanying drawing explanation:
accompanying drawing 1 is syntheti c route schema of the present invention.
accompanying drawing 2 is coupling agent modified Al
2
o
3
process flow sheet.
accompanying drawing 3 is coupling agent modified SiO
2
process flow sheet.
embodiment:
embodiment 1:
a kind of SiO
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the method comprises the steps:
(1) Al
2
o
3
and SiO
2
the modification of nanoparticle: use coupling agent KH-550 to nanometer Al
2
o
3
carry out modification, and with coupling agent KH-560 to nanometer SiO
2
carry out modification, the Al of modification
2
o
3
and SiO
2
as 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) prepare SiO
2
-Al
2
o
3
/ PU-EP nano composite material: add under the constant prerequisite of total amount at nanoparticle, with the nanometer SiO of different ratios
2
and Al
2
o
3
adopt the method for blend to change one's profession to PU-EP polymeric matrix, and prepare SiO
2
-Al
2
o
3
/ PU-EP nano composite material;
embodiment 2:
according to the SiO described in embodiment 1
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the Al that step (1) is described
2
o
3
and SiO
2
the method of the modification of nanoparticle is, with coupling agent KH-550 modified Nano Al
2
o
3
, get the nanometer Al that 3-5g is fully dry
2
o
3
with 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 regulates pH value, pH ≈ 3, and then standing 10min joins nanometer Al by the KH-550 mixed solution that regulates pH value
2
o
3
mixed solution in, temperature is to stir 4h in the thermostat water bath of 80 ℃, utilizes vacuum filtration pump suction filtration and by washing with alcohol, dry 3h under 60 ℃ of conditions, take out grind stand-by, KH-560 modified Nano SiO
2
, get the nanometer SiO that 4-5g is fully dry
2
with 80-100mL dehydrated alcohol, under the condition of 80 ℃, ultrasonic dispersion 0.5h.Get coupling agent KH-560 and the 40-50mL dehydrated alcohol of 0.1-0.5g, temperature is to stir 4h in the thermostat water bath of 80 ℃, utilizes vacuum filtration pump to carry out suction filtration and by washing with alcohol, 80 ℃ of dry 12h, take out grind stand-by.
embodiment 3:
according to the SiO described in embodiment 1
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the method of the preparation of the PU-EP system that step (2) is described is, by the epoxy resin E-51 of 10.00 g, get 2-4g urethane, epoxy resin and urethane are mixed, temperature is stirring reaction 1 h in the thermostat water bath of 80 ℃, then the temperature of water-bath is dropped to 50 ~ 55 ℃, add afterwards promotor imidazoles 0.01-0.02 g, and add solidifying agent methyl tetrahydro phthalic anhydride 7-9g, acid anhydrides consumption calculation formula is:
while having promotor to exist in reaction: K=1, by the formula of acid anhydrides consumption, calculate the actual amount of acid anhydrides, the concrete consumption of imidazoles promotor is the 0.1-0.2wt% of substrate ring epoxy resins quality, added after promotor imidazoles and solidifying agent acid anhydrides, continue stirring reaction 3 ~ 4 h, treat that promotor imidazoles dissolves completely in system, the epoxy resin reacting completely and polyurethane mixture are placed in vacuum filter air pump, remove the small bubbles in glue, the lacquer disk(-sc) that inwall is coated to releasing agent is put into baking oven preheating, then the glue reacting completely in beaker is evenly poured in lacquer disk(-sc) slowly, make smooth being layered on mould of glue, finally the lacquer disk(-sc) of completing being put into baking oven carries out gradient increased temperature and solidifies, curing process is: 80 ℃/2 h+120 ℃/1 h+150 ℃/1 h+180 ℃/1 h, finally make cured article PU-EP.
embodiment 4:
according to the SiO described in embodiment 1
2
-Al
2
o
3
the preparation method of/PU-EP matrix material, the SiO that step (1) is described
2
-Al
2
o
3
the preparation method of/PU-EP nano composite material is, in 50 mL beakers, add 10.00 g epoxy resin and 2-4g urethane, temperature is stirring reaction 1 h in the thermostat water bath of 80 ℃, after in system, epoxy resin and urethane mix, by the Al through KH-550 modification
2
o
3
with the SiO through KH-560 modification
2
-add wherein, in the thermostat water bath of 80 ℃, stirring reaction 1 h, treats nanometer SiO
2
-and nanometer Al
2
o
3
in system, be uniformly dispersed, the temperature of thermostat water bath drops to after 50-55 ℃, in system, add successively respectively solidifying agent methyl tetrahydro phthalic anhydride and promotor imidazoles again, stir about 1.5 h, treat that promotor imidazoles dissolves completely in system, the beaker reacting completely is placed in vacuum filter air pump, remove the small bubbles in glue, the lacquer disk(-sc) that inwall is coated to releasing agent is put into baking oven preheating, then the glue reacting completely in beaker is evenly poured in lacquer disk(-sc) slowly, make smooth being layered on mould of glue, finally the lacquer disk(-sc) of completing being put into baking oven carries out gradient increased temperature and solidifies, curing process is: 80 ℃/2 h+120 ℃/1 h+150 ℃/1 h+180 ℃/1 h, final curing obtains SiO2-Al2O3/PU-EP cured article.
embodiment 5:
the SiO preparing according to the method described in case study on implementation 1 or 2 or 3 or 4
2
--Al
2
o
3
/ PU-EP matrix material.
Claims (5)
1. a SiO
2-Al
2o
3the preparation method of/PU-EP matrix material, is characterized in that: the method comprises the steps:
(1) Al
2o
3and SiO
2the modification of nanoparticle: use coupling agent KH-550 to nanometer Al
2o
3carry out modification, and with coupling agent KH-560 to nanometer SiO
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) prepare SiO
2-Al
2o
3/ PU-EP nano composite material: add under the constant prerequisite of total amount at nanoparticle, with the nanometer SiO of different ratios
2and Al
2o
3adopt the method for blend to change one's profession to PU-EP polymeric matrix, and prepare SiO
2-Al
2o
3/ PU-EP nano composite material.
2. SiO according to claim 1
2-Al
2o
3the preparation method of/PU-EP matrix material, is characterized in that: the Al that step (1) is described
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 regulates pH value, pH ≈ 3, and then standing 10min joins nanometer Al by the KH-550 mixed solution that regulates pH value
2o
3mixed solution in, temperature is to stir 4h in the thermostat water bath of 80 ℃, utilizes vacuum filtration pump suction filtration and by washing with alcohol, dry 3h under 60 ℃ of conditions, take out grind stand-by, KH-560 modified Nano SiO
2, get the nanometer SiO that 4-5g is fully dry
2with 80-100mL dehydrated alcohol, under the condition of 80 ℃, ultrasonic dispersion 0.5h, get coupling agent KH-560 and the 40-50mL dehydrated alcohol of 0.1-0.5g, temperature is to stir 4h in the thermostat water bath of 80 ℃, utilize vacuum filtration pump to carry out suction filtration and use washing with alcohol, 80 ℃ of dry 12h, taking-up is ground stand-by.
3. SiO according to claim 1 and 2
2-Al
2o
3the preparation method of/PU-EP matrix material, it is characterized in that: the method for the preparation of the PU-EP system that step (2) is described is, by the epoxy resin E-51 of 10.00 g, get 2-4g urethane, epoxy resin and urethane are mixed, temperature is stirring reaction 1 h in the thermostat water bath of 80 ℃, then the temperature of water-bath is dropped to 50 ~ 55 ℃, add afterwards promotor imidazoles 0.01-0.02 g, and add solidifying agent methyl tetrahydro phthalic anhydride 7-9g, acid anhydrides consumption calculation formula is:
While having promotor to exist in reaction: K=1, by the formula of acid anhydrides consumption, calculate the actual amount of acid anhydrides, the concrete consumption of imidazoles promotor is the 0.1-0.2wt% of substrate ring epoxy resins quality, added after promotor imidazoles and solidifying agent acid anhydrides, continue stirring reaction 3 ~ 4 h, treat that promotor imidazoles dissolves completely in system, the epoxy resin reacting completely and polyurethane mixture are placed in vacuum filter air pump, remove the small bubbles in glue, the lacquer disk(-sc) that inwall is coated to releasing agent is put into baking oven preheating, then the glue reacting completely in beaker is evenly poured in lacquer disk(-sc) slowly, make smooth being layered on mould of glue, finally the lacquer disk(-sc) of completing being put into baking oven carries out gradient increased temperature and solidifies, curing process is: 80 ℃/2 h+120 ℃/1 h+150 ℃/1 h+180 ℃/1 h, finally make cured article PU-EP.
4. according to the SiO described in claim 1 or 2 or 3
2-Al
2o
3the preparation method of/PU-EP matrix material, is characterized in that: the SiO that step (1) is described
2-Al
2o
3the preparation method of/PU-EP nano composite material is, in 50 mL beakers, add 10.00 g epoxy resin and 2-4g urethane, temperature is stirring reaction 1 h in the thermostat water bath of 80 ℃, after in 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 ℃, stirring reaction 1 h, treats nanometer SiO
2-and nanometer Al
2o
3in system, be uniformly dispersed, the temperature of thermostat water bath drops to after 50-55 ℃, in system, add successively respectively solidifying agent methyl tetrahydro phthalic anhydride and promotor imidazoles again, stir about 1.5 h, treat that promotor imidazoles dissolves completely in system, the beaker reacting completely is placed in vacuum filter air pump, remove the small bubbles in glue, the lacquer disk(-sc) that inwall is coated to releasing agent is put into baking oven preheating, then the glue reacting completely in beaker is evenly poured in lacquer disk(-sc) slowly, make smooth being layered on mould of glue, finally the lacquer disk(-sc) of completing being put into baking oven carries out gradient increased temperature and solidifies, curing process is: 80 ℃/2 h+120 ℃/1 h+150 ℃/1 h+180 ℃/1 h, final curing obtains SiO2-Al2O3/PU-EP cured article.
5. the SiO preparing according to the method for claim 1 or 2 or 3 or 4
2--Al
2o
3/ PU-EP matrix material.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104262906A (en) * | 2014-09-26 | 2015-01-07 | 西安理工大学 | Nanometer filler cooperatively filling epoxy resin composite coating as well as preparation method and application thereof |
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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102816411A (en) * | 2011-06-10 | 2012-12-12 | 株式会社日立产机系统 | Electrical insulating material and high voltage equipment |
-
2014
- 2014-03-10 CN CN201410084954.5A patent/CN103951935B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102816411A (en) * | 2011-06-10 | 2012-12-12 | 株式会社日立产机系统 | Electrical insulating material and high voltage equipment |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104262906A (en) * | 2014-09-26 | 2015-01-07 | 西安理工大学 | Nanometer filler cooperatively filling epoxy resin composite coating as well as preparation method and application thereof |
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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