CN1417246A - In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material - Google Patents
In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material Download PDFInfo
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- CN1417246A CN1417246A CN 02150926 CN02150926A CN1417246A CN 1417246 A CN1417246 A CN 1417246A CN 02150926 CN02150926 CN 02150926 CN 02150926 A CN02150926 A CN 02150926A CN 1417246 A CN1417246 A CN 1417246A
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- Prior art keywords
- epoxy resin
- nano
- nanoparticle
- stir
- composite material
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 title abstract description 4
- 239000002086 nanomaterial Substances 0.000 title description 2
- 239000011246 composite particle Substances 0.000 title 1
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 9
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000010954 inorganic particle Substances 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 230000000621 autoagglutination Effects 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052901 montmorillonite Inorganic materials 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses an in-situ and inclusion polymerization process of preparing composite nano particle/epoxy resin material. The epoxy resin is biphenol A type epoxy resin; and the nano particle is nano SiO2, nano montmorillonite, nano TiO2, nano CaCO3 or nano ZnO. Via the in-situ polymerization and inclusion polymerization on the surface of nano inorganic particles, the inorganic nano particles with strong autoagglutination are dispersed homogeneously in epoxy resin matrix. The preparation process using water as solvent is simple, low in cost and less pollutant, needs no solvent recover equipment and is favorable to application in industry.
Description
Technical field
The present invention relates to the technology that a kind of original position and parcel polymerization prepare nanoparticle/epoxy resin composite material.
Technical background
Resins, epoxy is the important kind in the synthetic resins field, and it is celebrated with mechanical property, electric property and the adhesive property of excellence.At present, Resins, epoxy has been widely used in fields such as tackiness agent, coating, insulating material, structured material.In industry such as electric, machinofacture, aviation, boats and ships and Defence business, play an important role.China's Resins, epoxy develops rapidly since the nineties in 20th century, but throughput only accounts for 9% of world's overall throughput.It is bigger that China's Resins, epoxy industry and external advanced level are compared gap, is mainly reflected in that Technology is backward, kind is few, of poor quality, and low-and-medium-grade products is in the majority, especially extraordinary and functional product is less, can not satisfy domestic needs.
There are a lot of bibliographical informations Resins, epoxy to be carried out modification in recent years, can obviously improve performances such as its tensile strength, tensile modulus, shock strength with nano material.The bending of having reported exfoliated epoxy/18-Mont nano composite material as Lv Jiankun etc. (117 pages of " matrix material journal " the 19th the 1st phases of volume) and shock strength are compared with the Resins, epoxy of not filling nanoparticle when nano particle content is 2%～3% (wt) and have been improved 10% and 50% respectively.Dong Yuancai etc. (37 pages of " plastics industry " the 27 the 6th phases of volume) have reported with nano-TiO
2Resins, epoxy/nano-TiO for filler
2Matrix material, when the filling quality mark was 3%, the modulus in tension of material improved 370% than unmodified epoxy resin, drew Zhong Qiangdu to improve 44%, and shock strength improves 878%, and other performances also are significantly improved.Usually these modifications realize by inorganic nano-particle and the direct blend of Resins, epoxy; And often be difficult to inorganic particles is uniformly dispersed with this method; Especially when particle is nano level, because density and polar difference and the effect of nanoparticle intensive autohemagglutination, being difficult to reach real nanometer state disperses, there are many particulates to be in aggregating state, thereby make many advantages of nanoparticle modified epoxy resin composite not demonstrate fully out.People make the nanoparticle novel method of disperse in epoxy matrix material fully in exploration always.
Summary of the invention
For nanoparticle can be scattered in the epoxy matrix material with nano-scale, the invention provides the technology that a kind of original position and parcel polymerization prepare nanoparticle/epoxy resin composite material.
The objective of the invention is to realize by following technical scheme:
1, its technical process is:
1), dihydroxyphenyl propane and mass concentration be 5%～30% NaOH solution in the mol ratio of dihydroxyphenyl propane: NaOH are that 1: 1.1～1: 1.8 ratio is put into reactor, heat up and start and stir, 65 ℃～75 ℃ dissolvings down, be cooled to 50 ℃ then, add inorganic nano-particle, stir speed (S.S.) is controlled at 100～1500r/min, and nanoparticle is well dispersed in the medium;
2), drip epoxy chloropropane down at 50 ℃, dihydroxyphenyl propane: the mol ratio of epoxy chloropropane is 1: 1.1～1: 1.8, is warmed up to 80 ℃～95 ℃ after dropwising, and reaction 1.5～9hr injects cold water later on, treat to stop to stir after resin sinks, remove water, open and stir and injection hot water, inject cold water behind the stirring 15min, stop to stir and remove water, so repeat to equal to stop in 7 o'clock, carry out normal pressure dehydration and decompression dehydration drying then until pH value, must nanoparticle/epoxy resin composite material.
2, the Resins, epoxy that obtains is bisphenol A type epoxy resin.
3, nanoparticle is nanometer SiO
2Or nano imvite or nano-TiO
2Or nanometer CaCO
3Or nano-ZnO.
4, the add-on of nanoparticle accounts for 1%～30% of resin total mass.
The present invention compares with background technology, and the useful effect that has is: make the abundant disperse of inorganic nano-particle energy with extremely strong self aggregation effect in epoxy matrix material by in-situ polymerization and parcel polymerization; Take the method for a step washing prepare the technical process of nanoparticle/epoxy resin composite material simple, easy to operate, solvent recovery unit need be set, owing to make water make solvent, novel process is polluted few simultaneously, cost is low, helps industrial practical application.
Embodiment
Embodiment 1
1), 24.10 gram dihydroxyphenyl propanes and 51ml mass concentrations are that 10% NaOH solution joins in the 250ml round-bottomed flask, heat up also to start and stir, and 70 ℃ of dissolvings down, are cooled to 50 ℃ then, add 3 gram nanometer CaCO
3Particle, stir speed (S.S.) is controlled at 500r/min, and nanoparticle is well dispersed in the medium;
2), drip the 10ml epoxy chloropropane down at 50 ℃, 30min drips off, and is warming up to 80 ℃ after dropwising, and reaction 2hr injects cold water later on, treat that heavy the stopping in back stirs under the resin, remove water, open and stir and injection hot water, inject cold water behind the stirring 15min, stop to stir and remove water, so repeat to equal to stop in 7 o'clock, carry out normal pressure dehydration and decompression dehydration drying then until pH value, must nanometer CaCO
3/ epoxy resin composite material 27.97 grams.
Embodiment 2
1), 48.20 gram dihydroxyphenyl propanes and 65ml mass concentrations are that 15% NaOH solution joins in the 250ml round-bottomed flask, heat up also to start and stir, and 70 ℃ of dissolvings down, are cooled to 50 ℃ then, add 6 gram nanometer CaCO
3Particle, stir speed (S.S.) is controlled at 500r/min, and nanoparticle is well dispersed in the medium;
2), drip the 20ml epoxy chloropropane down at 50 ℃, 40min drips off, and is warming up to 90 ℃ after dropwising, and reaction 8hr injects cold water later on, treat that heavy the stopping in back stirs under the resin, remove water, open and stir and injection hot water, inject cold water behind the stirring 15min, stop to stir and remove water, so repeat to equal to stop in 7 o'clock, carry out normal pressure dehydration and decompression dehydration drying then until pH value, must nanometer CaCO
3/ epoxy resin composite material 55.56 grams.
Claims (4)
1, a kind of original position and parcel polymerization prepare the technology of nanoparticle/epoxy resin composite material; It is characterized in that:
1), dihydroxyphenyl propane and mass concentration be 5%～30% NaOH solution in the mol ratio of dihydroxyphenyl propane: NaOH are that 1: 1.1～1: 1.8 ratio is put into reactor, heat up and start and stir, 65 ℃～75 ℃ dissolvings down, be cooled to 50 ℃ then, add inorganic nano-particle, stir speed (S.S.) is controlled at 100～1500r/min, and nanoparticle is well dispersed in the medium;
2), drip epoxy chloropropane down at 50 ℃, dihydroxyphenyl propane: the mol ratio of epoxy chloropropane is 1: 1.1～1: 1.8, is warmed up to 80 ℃～95 ℃ after dropwising, and reaction 1.5～9hr injects cold water later on, treat to stop to stir after resin sinks, remove water, open and stir and injection hot water, inject cold water behind the stirring 15min, stop to stir and remove water, so repeat to equal to stop in 7 o'clock, carry out normal pressure dehydration and decompression dehydration drying then until pH value, must nanoparticle/epoxy resin composite material.
2, original position according to claim 1 and parcel polymerization prepare the technology of nanoparticle/epoxy resin composite material, it is characterized in that the Resins, epoxy that obtains is bisphenol A type epoxy resin.
3, original position according to claim 1 and parcel polymerization prepare the technology of nanoparticle/epoxy resin composite material, it is characterized in that nanoparticle is nanometer SiO
2Or nano imvite or nano-TiO
2Or nanometer CaCO
3Or nano-ZnO.
4, original position according to claim 1 and parcel polymerization prepare the technology of nanoparticle/epoxy resin composite material, it is characterized in that the add-on of nanoparticle accounts for 1%～30% of resin total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021509263A CN1186389C (en) | 2002-11-28 | 2002-11-28 | In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021509263A CN1186389C (en) | 2002-11-28 | 2002-11-28 | In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1417246A true CN1417246A (en) | 2003-05-14 |
| CN1186389C CN1186389C (en) | 2005-01-26 |
Family
ID=4751873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021509263A Expired - Fee Related CN1186389C (en) | 2002-11-28 | 2002-11-28 | In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1186389C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229700A (en) * | 2011-05-19 | 2011-11-02 | 安徽善孚新材料科技有限公司 | Epoxy resin nanometer montmorillonite composite material and preparation method thereof |
| CN102391620A (en) * | 2011-08-30 | 2012-03-28 | 西安交通大学 | Epoxy resin matrix nano-zinc oxide composite material and preparation method thereof |
| CN106751695A (en) * | 2016-12-06 | 2017-05-31 | 长江大学 | A kind of spherical gel particle and preparation method thereof |
| CN107446115A (en) * | 2016-06-01 | 2017-12-08 | 东北林业大学 | A kind of preparation method of nano modification bisphenol A type epoxy resin |
-
2002
- 2002-11-28 CN CNB021509263A patent/CN1186389C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229700A (en) * | 2011-05-19 | 2011-11-02 | 安徽善孚新材料科技有限公司 | Epoxy resin nanometer montmorillonite composite material and preparation method thereof |
| CN102229700B (en) * | 2011-05-19 | 2013-05-29 | 安徽善孚新材料科技有限公司 | Epoxy resin nanometer montmorillonite composite material and preparation method thereof |
| CN102391620A (en) * | 2011-08-30 | 2012-03-28 | 西安交通大学 | Epoxy resin matrix nano-zinc oxide composite material and preparation method thereof |
| CN107446115A (en) * | 2016-06-01 | 2017-12-08 | 东北林业大学 | A kind of preparation method of nano modification bisphenol A type epoxy resin |
| CN107446115B (en) * | 2016-06-01 | 2021-03-30 | 东北林业大学 | Preparation method of nano modified bisphenol A epoxy resin |
| CN106751695A (en) * | 2016-12-06 | 2017-05-31 | 长江大学 | A kind of spherical gel particle and preparation method thereof |
| CN106751695B (en) * | 2016-12-06 | 2018-11-06 | 长江大学 | A kind of spherical gel particle and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1186389C (en) | 2005-01-26 |
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