CN100334124C - Organic imvite modified epoxyresin - Google Patents
Organic imvite modified epoxyresin Download PDFInfo
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- CN100334124C CN100334124C CNB2005100224126A CN200510022412A CN100334124C CN 100334124 C CN100334124 C CN 100334124C CN B2005100224126 A CNB2005100224126 A CN B2005100224126A CN 200510022412 A CN200510022412 A CN 200510022412A CN 100334124 C CN100334124 C CN 100334124C
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- Prior art keywords
- organo montmorillonite
- epoxy
- epoxy resin
- imvite modified
- organic solvent
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 33
- -1 C12 ester Chemical class 0.000 claims abstract description 58
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 58
- 239000004593 Epoxy Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 10
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 7
- ZCPCLAPUXMZUCD-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC ZCPCLAPUXMZUCD-UHFFFAOYSA-M 0.000 claims description 4
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 4
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 claims description 4
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- GZTMDLIDGQGZFL-UHFFFAOYSA-M [Cl-].[NH4+].C(C1=CC=CC=C1)C(C1=CC=CC=C1)[N+](C)(C)CCCCCCCCCCCCCCCC.[Cl-] Chemical compound [Cl-].[NH4+].C(C1=CC=CC=C1)C(C1=CC=CC=C1)[N+](C)(C)CCCCCCCCCCCCCCCC.[Cl-] GZTMDLIDGQGZFL-UHFFFAOYSA-M 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 229910017059 organic montmorillonite Inorganic materials 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract 1
- 238000005325 percolation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 241000446313 Lamella Species 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000004760 silicates Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention uses o-phthalic acid C4 to C12 ester which is a non-volatile organic solvent for expanding organic montmorillonite and adding the expanded organic montmorillonite into bisphenol-A epoxy resin (E51) with a certain proportion. The dispersing technology in a percolation type is used for agitation and mix for effectively stripping the nanometer sheet layers of the organic montmorillonite and uniformly dispersing the nanometer sheet layers into epoxy resin. Thus, the strength and the toughness of the modified epoxy resin of the organic montmorillonite are increased, and the nanometer epoxy resin with excellent performance is finally prepared. The modified epoxy resin is used as the main body material of adhesive, and the adhering strength, the wet, hot and aging resistance, and other integrated properties of the main body material are obviously increased in order to provide the technical basis for preparing the nanometer epoxy resin adhesive of high performance to be suitable for the high requirements of each field.
Description
Technical field
The present invention relates to a kind of organic imvite modified epoxyresin, belong to chemical technology field.
Background technology
Resins, epoxy is a kind of general synthetic materials with good bonding, erosion resistance, insulativity and the more high performance of mechanical strength, be to use the most general thermoset basis resin in the strongthener field, be widely used in the manufacturing of matrix materials such as tackiness agent, protective system, insulating material.But because some Resins, epoxy weathering resistance and toughness commonly used are relatively poor, the application of simple ring epoxy resins is subjected to certain restriction.Method of modifying by suitable can make its performance be improved to a certain extent.In existing method of modifying, adopt the rubber toughened modified epoxy that comes more, but its intensity and rigidity are descended.Introducing nano material in Resins, epoxy is a kind of effective modification mode, because the high reactivity of nano material, bigger serface, strong interface effect make the over-all properties of Resins, epoxy be improved.The nano material of Cai Yonging mostly is nano-powder now, as nano silicon, nano titanium oxide etc., but because the material that these commodity particle diameters have a nanoscale is reunited easily, realizes the suitable difficulty of nano-dispersed truly in Resins, epoxy.And the polynite that is called as natural nano-material is a kind of silicate with laminate structure, and its structure lamella all has nanoscale.The sheet interlayer has tradable Na
+, Ca
2+, Mg
2+Or Al
3+Deng positively charged ion, pass through ion exchange reaction, processing promptly organises, can introduce the organic ion bigger than above-mentioned ion volume, the interlamellar spacing of montmorillonite layer is strengthened, the interlayer that polymerisable monomer is entered strut, and then, the structure lamella with nanoscale is disperseed in polymkeric substance because of monomer polymerization further increases interlamellar spacing even dissociates; Perhaps with the process of Mixing of Polymer Melt, because of the effect of strong shearing force, heating power etc., the nano-scale structures limellar stripping of organo montmorillonite also is dispersed in the polymeric matrix, thereby forms nano composite polymer/laminated silicate material.This intercalation compounding technology can realize that organism matrix and inorganics disperse phase are really compound on nanoscale, and resulting nano composite material can ideally combine rigidity, dimensional stability and the thermostability of inorganics and toughness, workability and the dielectricity of polymkeric substance.
It seems from numerous researchs reports of relevant Resins, epoxy (EP)/Nano composite material of montmorillonite in recent years, stress in the experimental study of tackiness agent more, as Tian Baoyong etc., the preparation method of Epoxy Resin nano composite material (Hebei Academy of Sciences journal, 2002,19 (4) 247～249), Jiao Jian etc., it is (bonding that graft process prepares the research of Epoxy Resin nano composite material, 2004,25 (2) 23～26) and patent documentation CN98120153.9, CN98120123.7, CN01136947.7, US6251980 etc.Make a general survey of existing technology, be mostly with organo montmorillonite on non-swelling basis, under the effect of heating power and shearing force, compound through intercalation, make organic montmorillonite nano yardstick limellar stripping and be scattered in the epoxy-resin systems, thus preparation organo montmorillonite/epoxy resin nano composites; Perhaps, organo montmorillonite is joined in the Resins, epoxy of solvent cut, after intercalation was compound, other materials such as interpolation solidifying agent prepared nano composite material; Perhaps, organo montmorillonite is added after the swelling in volatile solvent in the Resins, epoxy (or its solution) and again solvent is removed behind the mixing.About Resins, epoxy being carried out some gordian techniquies of modification, as choice of Solvent, organo montmorillonite effectively peeling off and homodisperse shorter mention then in Resins, epoxy.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, organic imvite modified epoxyresin of a kind of excellent performance and preparation method thereof is provided, particularly when Resins, epoxy is carried out modification choice of Solvent, organo montmorillonite in Resins, epoxy effectively peel off and gordian technique such as homodisperse provides a solution.
Flow-through type dispersion technology system adopts special flow-through type reactor (CN88219019.9, CN98229551.0, CN99232127.1, CN01256487.7), make fluid under the agitating vane effect of high speed rotating, the some apertures that pass on the blade produce countless jets, brute force is torn the original state of fluid, changed the tradition process that mixes and reached elimination Δ c (concentration difference) by the diffusion of macroscopic view mixing generation eddy current, Δ t (temperature head), the mechanism process of Δ e (energy difference), directly produce the diffusion of intensive eddy current by the jet entrainment process, be formed on the abundant contact of (even on nanoscale) various ingredients on the microsize, set up new energy field, realization arises from the microcosmic desirable uniform mixing of macroscopic finally, and plays tangible energy-conserving action.The flow-through type dispersion technology is particularly useful for heterogeneous homodisperse technical requirements in the high viscosity fluid.
The present invention utilizes this dispersion technology of flow-through type efficiently in the preparation process of organic imvite modified epoxyresin, and concrete technical scheme is as follows:
Organic imvite modified epoxyresin of the present invention, by component epoxy (E51), organo montmorillonite and non-volatile organic solvent are formed, and the weight ratio between each component is Resins, epoxy (E51): organo montmorillonite: non-volatile organic solvent=100: 0.5～10: 5～40.Wherein, organo montmorillonite is to carry out ion exchange reaction by a kind of in the quaternary ammonium salts such as polynite and distearyl dimethyl ammonium chloride, Varisoft 432PPG, octadecyl trimethyl ammonium chloride, benzyl hexadecyldimethyl benzyl ammonium ammonium chloride and make.Non-volatile organic solvent is phthalic acid C
4～C
12Ester is as a kind of solvent in dibutyl phthalate and the dioctyl phthalate (DOP) or the mixing solutions of multiple solvent.
The preparation method of organic imvite modified epoxyresin of the present invention is:
(1) swelling of organo montmorillonite and grinding: non-volatile organic solvent is added to fully infiltration in the organo montmorillonite by corresponding proportioning, mixes, left standstill 48～96 hours, be ground to 15～40 μ m through shredder again.
(2) preparation of organic imvite modified epoxyresin: swelling is mixed by corresponding proportioning with Resins, epoxy (E51) with the organo montmorillonite that ground, and join in the flow-through type agitator, be warming up to 40～90 ℃, the control stirring velocity is 1000～2400r/min, reacts 0.5～4 hour.
The present invention is through testing, test discovery repeatedly, with organo montmorillonite at specific non-volatile solvents phthalic acid C
4～C
12Ester after swelling in the mixing solutions of a kind of solvent in dibutyl phthalate and the dioctyl phthalate (DOP) or multiple solvent, can promote organo montmorillonite effectively peeling off and homodisperse in epoxy resin-base.
The dispersion of organo montmorillonite is a great problem of nano material preparation technology always, how organic montmorillonite nano structure lamella effectively peeled off and homodisperse, and be the key point that preparation has the high-performance epoxy resin of nano effect.The present invention has introduced the flow-through type dispersion technology, has increased in the preparation process, by non-volatile solvents phthalic acid C
4～C
12The contact area of ester swollen organo montmorillonite and epoxy resin-base, strengthened dispersion effect, organo montmorillonite lamella after the swelling can effectively be peeled off and homodisperse in Resins, epoxy, thereby improve the intensity of modified epoxy, improve its toughness, finally prepare the more excellent organic imvite modified epoxyresin of performance.
Compare with unmodified epoxy resin, organic imvite modified epoxyresin of the present invention has also improved the intensity of modified epoxy improving its flexible simultaneously.As the A component, is B component with the polyamine curing agent with product of the present invention, and the tackiness agent that is mixed with has good comprehensive performances, is in particular in (with comparing without organic imvite modified Resins, epoxy):
(1) tensile strength significantly improves.
(2) shearing resistance is largely increased.
(3) solid substance does not have obvious crest through wide-angle X diffraction experiment test, illustrates that the organo montmorillonite lamella effectively peels off and be scattered in the matrix resin.
Concrete data see Table 1.
Table 1 organic imvite modified epoxyresin tackiness agent performance relatively
| Numbering | Organo montmorillonite add-on (weight ratio) | Tensile strength (Mpa) | Shearing resistance (Mpa) |
| 0 | Blank sample | 19.6 | 6.6 |
| 1 | 1％ | 11.0 | 11.3 |
| 2 | 3％ | 24.0 | 9.4 |
| 3 | 5％ | 28.7 | 16.1 |
| 4 | 7％ | 30.7 | 15.5 |
| 5 | 9％ | 27.1 | 15.1 |
Embodiment
Embodiment 1
(1) swelling of organo montmorillonite
With the 250g dibutyl phthalate, slowly join 100g in the organo montmorillonite that distearyl dimethyl ammonium chloride was handled, stir, organo montmorillonite is fully soaked into, and uniform mixing, leave standstill 72 hours, after shredder is ground to about 25 μ m.
(2) preparation of organic imvite modified epoxyresin
99g Resins, epoxy E51 is joined in the flow-through type reactor, stirring also is warming up to 70+5 ℃, organo montmorillonite after the adding net weight 1g swelling, the control stirring velocity is 1400r/min, constant temperature stirred 45 minutes, make organo montmorillonite thorough mixing in epoxy resin-base, promptly get the modified epoxy of organo montmorillonite add-on 1%.
Embodiment 2
(1) swelling of organo montmorillonite
With the 250g dibutyl phthalate, slowly join in the organo montmorillonite that the 100g Varisoft 432PPG handled, stir, organo montmorillonite is fully soaked into, and uniform mixing, leave standstill 72 hours, after shredder is ground to about 25 μ m.
(2) preparation of organic imvite modified epoxyresin
97g Resins, epoxy E51 is joined in the flow-through type reactor, stirring also is warming up to 70+5 ℃, organo montmorillonite after the adding net weight 3g swelling, the control stirring velocity is 1400r/min, constant temperature stirred 45 minutes, make organo montmorillonite thorough mixing in epoxy resin-base, promptly get the modified epoxy of organo montmorillonite add-on 3%.
Embodiment 3
(1) swelling of organo montmorillonite
With the 250g dioctyl phthalate (DOP), slowly join in the organo montmorillonite that the 100g distearyl dimethyl ammonium chloride handled, stir, organo montmorillonite is fully soaked into, and uniform mixing, leave standstill 72 hours, after shredder is ground to about 25 μ m.
(2) preparation of organic imvite modified epoxyresin
95g Resins, epoxy E51 is joined in the flow-through type reactor, stirring also is warming up to 70+5 ℃, organo montmorillonite after the adding net weight 5g swelling, the control stirring velocity is 1400r/min, constant temperature stirred 45 minutes, make organo montmorillonite thorough mixing in epoxy resin-base, promptly get organo montmorillonite add-on 5% modified epoxy.
Embodiment 4
(1) swelling of organo montmorillonite
With the 250g dioctyl phthalate (DOP), slowly join in the organo montmorillonite that the 100g octadecyl trimethyl ammonium chloride handled, stir, organo montmorillonite is fully soaked into, and uniform mixing, leave standstill 72 hours, after shredder is ground to about 25 μ m.
(2) preparation of organic imvite modified epoxyresin
93g Resins, epoxy E51 is joined in the flow-through type reactor, stirring also is warming up to 70+5 ℃, organo montmorillonite after the adding net weight 7g swelling, the control stirring velocity is 1400r/min, constant temperature stirred 45 minutes, make organo montmorillonite thorough mixing in epoxy resin-base, promptly get organo montmorillonite add-on 7% modified epoxy.
Embodiment 5
(1) swelling of organo montmorillonite
With the 250g dibutyl phthalate, slowly join in the organo montmorillonite that the 100g Varisoft 432PPG handled, stir, organo montmorillonite is fully soaked into, and uniform mixing, leave standstill 72 hours, after shredder is ground to about 25 μ m.
(2) preparation of organic imvite modified epoxyresin
91g Resins, epoxy E51 is joined in the flow-through type reactor, stirring also is warming up to 70+5 ℃, organo montmorillonite after the adding net weight 9g swelling, the control stirring velocity is 1400r/min, constant temperature stirred 45 minutes, make organo montmorillonite thorough mixing in epoxy resin-base, promptly get organo montmorillonite add-on 9% modified epoxy.
Claims (3)
1. organic imvite modified epoxyresin, it is characterized in that by component epoxy E51, organo montmorillonite, form with non-volatile organic solvent, weight ratio between each component is Resins, epoxy E51: organo montmorillonite: non-volatile organic solvent=100: 0.5～10: 5～40, wherein, organo montmorillonite is by polynite and distearyl dimethyl ammonium chloride, Varisoft 432PPG, octadecyl trimethyl ammonium chloride, a kind of in the quaternary ammonium salt of benzyl hexadecyldimethyl benzyl ammonium ammonium chloride carries out ion exchange reaction and makes, and non-volatile organic solvent is phthalic acid C
4～C
12The mixing solutions of one or more solvents in the ester.
2. organic imvite modified epoxyresin according to claim 1 is characterized in that described non-volatile organic solvent is the mixing solutions of one or both solvents in dibutyl phthalate and the dioctyl phthalate (DOP).
3. according to the preparation method of the described organic imvite modified epoxyresin of claim 1, it is characterized in that:
(1) swelling of organo montmorillonite and grinding: non-volatile organic solvent is added to fully infiltration in the organo montmorillonite by corresponding proportioning, mixes, left standstill 48～96 hours, be ground to 15～40 μ m through shredder again;
(2) preparation of organic imvite modified epoxyresin: swelling is mixed by corresponding proportioning with Resins, epoxy E51 with the organo montmorillonite that ground, and join in the flow-through type agitator, be warming up to 40～90 ℃, the control stirring velocity is 1000～2400r/min, reacted 0.5～4 hour, and promptly got the organic imvite modified epoxyresin finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100224126A CN100334124C (en) | 2005-12-27 | 2005-12-27 | Organic imvite modified epoxyresin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100224126A CN100334124C (en) | 2005-12-27 | 2005-12-27 | Organic imvite modified epoxyresin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793195A CN1793195A (en) | 2006-06-28 |
| CN100334124C true CN100334124C (en) | 2007-08-29 |
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|---|---|---|---|
| CNB2005100224126A Expired - Fee Related CN100334124C (en) | 2005-12-27 | 2005-12-27 | Organic imvite modified epoxyresin |
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| CN105623197A (en) * | 2016-04-08 | 2016-06-01 | 章俊 | Epoxy resin (EP) nano plastic and preparation method thereof |
| CN107507692A (en) * | 2017-10-10 | 2017-12-22 | 徐州赛欧电子科技有限公司 | A kind of frame vertical transformer of antirust radiating |
| CN109161076A (en) * | 2018-07-26 | 2019-01-08 | 徐州辛辛那提新型材料有限公司 | A kind of preparation process of high impact properties anti-corrosion lightweight PE solid wall pipe |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017632A (en) * | 1996-06-17 | 2000-01-25 | Claytec, Inc. | Hybrid organic-inorganic nanocomposites and methods of preparation |
| CN1250064A (en) * | 1998-10-06 | 2000-04-12 | 中国科学院化学研究所 | Preparation of epoxy resin/montmorillonoid intercalation composite material |
| CN1250790A (en) * | 1998-10-13 | 2000-04-19 | 中国科学院化学研究所 | Antiflowing epoxy resin/mentmorillonite compound and its preparing process |
| JP2000202937A (en) * | 1999-01-14 | 2000-07-25 | Toppan Printing Co Ltd | Vapor deposition film laminated packaging material |
| CN1354198A (en) * | 2001-12-26 | 2002-06-19 | 河北工业大学 | Epoxy resin/montmorillonoid nano-compoiste-material and its preparation method |
-
2005
- 2005-12-27 CN CNB2005100224126A patent/CN100334124C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017632A (en) * | 1996-06-17 | 2000-01-25 | Claytec, Inc. | Hybrid organic-inorganic nanocomposites and methods of preparation |
| CN1250064A (en) * | 1998-10-06 | 2000-04-12 | 中国科学院化学研究所 | Preparation of epoxy resin/montmorillonoid intercalation composite material |
| CN1250790A (en) * | 1998-10-13 | 2000-04-19 | 中国科学院化学研究所 | Antiflowing epoxy resin/mentmorillonite compound and its preparing process |
| JP2000202937A (en) * | 1999-01-14 | 2000-07-25 | Toppan Printing Co Ltd | Vapor deposition film laminated packaging material |
| CN1354198A (en) * | 2001-12-26 | 2002-06-19 | 河北工业大学 | Epoxy resin/montmorillonoid nano-compoiste-material and its preparation method |
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| Publication number | Publication date |
|---|---|
| CN1793195A (en) | 2006-06-28 |
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