CN103525003B - Low-temperature plasma modified aluminum oxide enhanced phenolic resin and preparation method thereof - Google Patents
Low-temperature plasma modified aluminum oxide enhanced phenolic resin and preparation method thereof Download PDFInfo
- Publication number
- CN103525003B CN103525003B CN201310486001.7A CN201310486001A CN103525003B CN 103525003 B CN103525003 B CN 103525003B CN 201310486001 A CN201310486001 A CN 201310486001A CN 103525003 B CN103525003 B CN 103525003B
- Authority
- CN
- China
- Prior art keywords
- resol
- al2o3
- phenolic resin
- low
- plasma
- Prior art date
- 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.)
- Expired - Fee Related
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses low-temperature plasma modified aluminum oxide enhanced phenolic resin and a preparation method thereof. The enhanced phenolic resin consists of the following components in parts by weight: 100 parts of phenolic resin, 1 to 30 parts of plasma modified aluminum oxide (Al2O3), 8 parts of hexamethylenetetramine, 100 to 150 parts of acetone and 100 to 150 parts of rosin water, wherein the plasma modified Al2O3 is prepared by adopting an acetone organic source and carrying out surface modification on Al2O3 particles through plasma generated by discharging of direct current. The Al2O3 particles are subjected to surface modification by adopting the acetone organic source and generating plasma through discharging of direct current, and one layer of polymer film or group which is combined with the polymer well is deposited on the surface of the treated Al2O3 powder, so that the dispersibility and the wettability of the Al2O3 particles in the phenolic resin can be improved, and the mechanical and thermal properties of a Al2O3/phenolic resin-based composite material are further improved.
Description
Technical field
The present invention relates to field of compound material adopts low-temperature plasma modified aluminum oxide to strengthen resol and preparation method thereof.
Background technology
Resol belongs to organic polymer material, day by day severe along with applying working condition, has higher requirement, need carry out modification to pure phenolic resin to its performance.Current method of modifying is roughly divided into three classes, comprises organically-modified, inorganic modified and composite modified.Wherein organically-modified main organic blended, the polymer blending having different performance as added, filling organism ultrafine particle are as Modification of Phenolic Resin By Elastomeric Nanoparticles of Nitrile Butadiene, and also available cashew nut shell oil, tung oil, flax wet goods thermoplastics and the good polymkeric substance of thermotolerance are if polyimide, bismaleimides etc. are to phenolic resin modified; It is inorganic modified that to comprise inorganic multivariate acid modification as filling-modified in boric acid, inorganic particle or rigid particles etc.; Composite modified is organic blended and inorganic modified method combined, in resol, blended reaching toughness reinforcing object by organic as adding thermoplastic polymer, filling inorganic particulate simultaneously or adding inorganic multivariate acid and improving thermotolerance and the mechanical strength of resol in resol.
Compare other modified particles, Al2O3 is a kind of inorganic ceramic material cheap and easy to get, it has that hardness is high, wear resisting property and the advantage such as thermal stability is good, contribute to the intensity of raising resin, hardness, wear resisting property and resistance to elevated temperatures, but bonding force and the dispersion effect of Al2O3 and resin are bad, make mechanical strength of resin not reach service requirements.Now in order to increase the bonding force of Al2O3 particle and resin, conventional coupling agent carries out modification to Al2O3 particle surface, coupling agent modified enhanced mechanism is that Al2O3 particle forms physical crosslinking after surface treatment and between resol molecular chain, add the point of the commissure after phenolic resin curing, adsorb the uniform particles distribution of many bar molecular chains, can all separate loading thus less fracture possibility well, reach the effect of enhancing.But resin property modified by this method depends primarily on coupling agent, the coupling agent limitednumber that market is sold.
Plasma body refers to part or all of ionized gas, is made up of the particulate such as unbound electron, ion, is macroscopically electric neutrality, and the 4th state that plasma body exists as material is by people are familiar with, and plasma technique has entered practical application area widely.Plasma body is divided into high-temperature plasma and low-temperature plasma by domestic scholars, wherein, the specific ionization of low-temperature plasma is lower, belong to nonthermal plasma, there is a large amount of, that kind is more, activity is stronger particle, easily react with contacted material surface, have cost low, without the remarkable advantage such as waste, no pollution.In plasma reactor, a small amount of organic monomer molecular discharge is excited by high frequency, alternating current-direct current, microwave homenergic, under the bombardment collision of electronics, organic monomer molecule continues to occur to activate ionization, generation free radical and body material react, and can produce new modified group at material surface.
Summary of the invention
The object of the present invention is to provide low-temperature plasma modified aluminum oxide to strengthen resol, adopt acetone plasma body to carry out modification to Al2O3 particle surface, make Al2O3 particle have better bonding force and consistency, the shearing resistance of resol is improved greatly.
Another object of the present invention is to provide low-temperature plasma modified aluminum oxide to strengthen the preparation method of resol, the method principle is reliable, easy and simple to handle, and it is extensive that the Al2O3 used strengthens particle source, and inexpensive is easy to get, and has wide market outlook.
For reaching above technical purpose, the invention provides following technical scheme.
The present invention adopts the organic source of acetone, produce plasma body by direct-current discharge and surface modification is carried out to Al2O3 particle, Al2O3 powder surface deposition one layer of polymeric film after process or group good with polymkeric substance associativity, the dispersiveness of Al2O3 particle between resol, wetting property can be improved, thus improve the performance such as mechanics, calorifics of Al2O3/ phenolic resin-base composite further.
Low-temperature plasma modified Al2O3 strengthens resol, consists of the following composition: 100 parts by weight of phenolic resin, 1-30 weight part plasma modification Al2O3,8 weight part hexamethylenetetramines, 100-150 pbw acetone and 100-150 weight part rosin; Described plasma modification Al2O3 adopts the organic source of acetone, carries out surface modification form by direct-current discharge generation plasma body to Al2O3 particle.
Low-temperature plasma modified Al2O3 strengthens the preparation method of resol, comprises the following steps successively:
1) Al2O3's is low-temperature plasma modified
Al2O3 is put into low-temperature plasma generating unit to process, regulate the flow 45-65 ml/ min of acetone gas, the treatment temp of control device is at 50-80 DEG C, pressure is 0. 12-10 Pa, voltage is between 3KV-30KV, Cement Composite Treated by Plasma power should control between 300-450 W, and the treatment time is 3-5min.
2) the adding of solidifying agent
8 weight part hexamethylenetetramines are added in 100 parts by weight of phenolic resin, constantly stir in 40-60 DEG C of water-bath, hexamethylenetetramine and resol are fully mixed.
3) dilution of resol
100-150 pbw acetone and 100-150 weight part rosin are added to step 2) resol in, slowly stir in 40 DEG C of water-baths, until resol dissolves completely.
4) the mixing of resol after modified Al2O3 and dilution
Low-temperature plasma modified for 1-30 weight part Al2O3 is added in the resol after step 3) dilution, in ultrasonic wave, disperse 0.5h.
5) solidify
The solution of step 4) is solidified 4-5 hour in 50-100 DEG C of baking oven, takes out after cooling.
The resol that the present invention uses, aluminum oxide, hexamethylenetetramine, acetone, rosin are commercially available, aluminum oxide grain size diameter 100nm ~ 1.0 μm.
Compared with prior art, the present invention has following beneficial effect:
1) the present invention adopts acetone plasma body to carry out modification to Al2O3 particle surface, Al2O3 particle surface is made to deposit one layer of polymeric, the inorganic gass such as ratio O2, N2 are that plasma modification Al2O3 particle has better bonding force and consistency, and the shearing resistance of modified resol is improved greatly;
2) the present invention not only can adopt acetone plasma modification Al2O3 particle, as long as organism that is good with phenolic compatible, that vaporize in vacuum or heated condition energy can be used as plasma body carry out Modification on Al 2O3 particle, modification time is short, and efficiency is high;
3) it is extensive that the Al2O3 that the present invention is used strengthens particle source, and inexpensive is easy to get;
4) making thinner with acetone and rosin, making resol smooth surface bubble-free when solidifying.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that plasma modification Al2O3 strengthens resol.
Embodiment
Embodiment 1
0.63g Al2O3 is put into low-temperature plasma generating unit process, regulate the flow 51 m L/ min of acetone, pressure is 4 Pa, voltage is 20KV, Cement Composite Treated by Plasma power should control at 350 W, and the treatment temp of device is at 60 DEG C, and the treatment time is 3min.
0.24g hexamethylenetetramine is added in 3g resol, fully mixes.
3.5ml acetone and 3.5ml rosin are added in the resol of fully mixing, slowly stir in 40 DEG C of water-baths, until resol dissolves completely.
Low-temperature plasma modified for 0.63g Al2O3 is added in the resol after dilution, is sprayed on 20CrMoNi steel surface disperse half hour in ultrasonic wave after, solidifies 4 hours in 60 DEG C of baking ovens.
Require the tensile shear strength of test compound material according to GB7124-86, the shearing resistance recording phenolic resin composite is 32.18MPa.
Embodiment 2
0.63g Al2O3 is put into plasma producing apparatus process, regulate the flow 51 m L/ min of acetone, pressure is 5 Pa; , voltage is 20KV, and Cement Composite Treated by Plasma power should control at 350 W, and the treatment temp of device is at 60 DEG C; Treatment time is 3min.
0.24g hexamethylenetetramine is added in 3g resol, fully mixes.
3.5ml acetone and 3.5ml rosin are added in the resol of fully mixing, slowly stir in 40 DEG C of water-baths, until resol dissolves completely.
Low-temperature plasma modified for 0.63g Al2O3 is added in the resol after dilution, is sprayed on 20CrMoNi steel surface disperse half hour in ultrasonic wave after, solidifies 4 hours in 60 DEG C of baking ovens.
The shearing resistance recording modified phenolic resin composite is 35.28MPa.
Embodiment 3
0.15g Al2O3 is put into plasma producing apparatus process, regulate the flow 51 m L/ min of acetone, pressure is 5 Pa; , voltage is 20KV, and Cement Composite Treated by Plasma power should control at 350 W, and the treatment temp of device is at 60 DEG C; Treatment time is 3min.
0.24g hexamethylenetetramine is added in 3g resol, fully mixes.
3.5ml acetone and 3.5ml rosin are added in the resol of fully mixing, slowly stir in 40 DEG C of water-baths, until resol dissolves completely.
Low-temperature plasma modified for 0.15g Al2O3 is added in the resol after dilution, is sprayed on 20CrMoNi steel surface disperse half hour in ultrasonic wave after, solidifies 4 hours in 60 DEG C of baking ovens.
The shearing resistance recording modified phenolic resin composite is 33.71MPa.
Claims (2)
1. low-temperature plasma modified aluminum oxide strengthens resol, consists of the following composition: 100 parts by weight of phenolic resin, 1-30 weight part plasma modification Al
2o
3, 8 weight part hexamethylenetetramines, 100-150 pbw acetone and 100-150 weight part rosin; Described plasma modification Al
2o
3prepared by following process: by Al
2o
3put into low-temperature plasma generating unit to process, regulate the flow 45-65mL/min of acetone gas, the treatment temp of control device is at 50-80 DEG C, pressure is 0.12-10Pa, voltage is between 3kV-30kV, and Cement Composite Treated by Plasma power controls between 300-450W, and the treatment time is 3-5min.
2. low-temperature plasma modified aluminum oxide as claimed in claim 1 strengthens the preparation method of resol, comprises the following steps successively:
1) by Al
2o
3put into low-temperature plasma generating unit to process, regulate the flow 45-65mL/min of acetone gas, the treatment temp of control device is at 50-80 DEG C, pressure is 0.12-10Pa, voltage is between 3kV-30kV, and Cement Composite Treated by Plasma power controls between 300-450W, and the treatment time is 3-5min;
2) 8 weight part hexamethylenetetramines are added in 100 parts by weight of phenolic resin, constantly stir in 40-60 DEG C of water-bath, hexamethylenetetramine and resol are fully mixed;
3) 100-150 pbw acetone and 100-150 weight part rosin are added to step 2) resol in, slowly stir in 40 DEG C of water-baths, until resol dissolves completely;
4) by low-temperature plasma modified for 1-30 weight part Al
2o
3add step 3) dilution after resol in, in ultrasonic wave, disperse 0.5h;
5) by step 4) solution in 50-100 DEG C of baking oven, solidify 4-5 hour, cooling after take out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310486001.7A CN103525003B (en) | 2013-10-17 | 2013-10-17 | Low-temperature plasma modified aluminum oxide enhanced phenolic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310486001.7A CN103525003B (en) | 2013-10-17 | 2013-10-17 | Low-temperature plasma modified aluminum oxide enhanced phenolic resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103525003A CN103525003A (en) | 2014-01-22 |
| CN103525003B true CN103525003B (en) | 2015-04-08 |
Family
ID=49927375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310486001.7A Expired - Fee Related CN103525003B (en) | 2013-10-17 | 2013-10-17 | Low-temperature plasma modified aluminum oxide enhanced phenolic resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103525003B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366345B (en) * | 2016-08-26 | 2018-11-27 | 西安理工大学 | The method of coupling agent and the composite modified micron aluminum oxide of plasma |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343397A (en) * | 2008-08-22 | 2009-01-14 | 常熟东南塑料有限公司 | Halogen-free flame-proof phenolic plastic |
| CN102002883A (en) * | 2010-09-20 | 2011-04-06 | 华南理工大学 | Wet type paper-based friction material as well as preparation method and application thereof |
| CN102391818A (en) * | 2011-09-29 | 2012-03-28 | 秦会斌 | Insulated thermal conductive adhesive and preparation method thereof |
-
2013
- 2013-10-17 CN CN201310486001.7A patent/CN103525003B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343397A (en) * | 2008-08-22 | 2009-01-14 | 常熟东南塑料有限公司 | Halogen-free flame-proof phenolic plastic |
| CN102002883A (en) * | 2010-09-20 | 2011-04-06 | 华南理工大学 | Wet type paper-based friction material as well as preparation method and application thereof |
| CN102391818A (en) * | 2011-09-29 | 2012-03-28 | 秦会斌 | Insulated thermal conductive adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103525003A (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jing et al. | Surface modification of carbon fibers and the selective laser sintering of modified carbon fiber/nylon 12 composite powder | |
| CN108035143B (en) | Method for simultaneously improving interface strength and toughness of carbon fiber epoxy composite material | |
| Niu et al. | Mechanical and thermal properties of PEEK composites by incorporating inorganic particles modified phosphates | |
| Wu et al. | Effect of a vinyl ester-carbon nanotubes sizing agent on interfacial properties of carbon fibers reinforced unsaturated polyester composites | |
| CN109251051B (en) | Carbon nanofiber reinforced pantograph composite carbon sliding plate and preparation method thereof | |
| CN108641288A (en) | A kind of nano zircite/epoxy resin composite material and preparation method thereof | |
| CN107354421B (en) | A kind of preparation method of graphene-copper-amorphous composite coating | |
| CN101875779A (en) | Polyamide/nano expanded graphite/carbon fiber high-strength conducting composite material and preparation method thereof | |
| CN106591822A (en) | Preparation method and application of graphene strengthened copper base composite coating | |
| CN103613883A (en) | Wear-resistant hard composite material using graphene as filler and preparation method thereof | |
| CN109574696A (en) | A kind of resistance to electric arc Material for Pantograph Slide of high intensity and preparation method thereof | |
| CN102796374A (en) | Carbon nanotube/benzoxazine/bimaleimide composite material and preparation method thereof | |
| CN108641356A (en) | Graphene/class graphene WS of three phosphonitrilic polymer of ring modification2/ Bismaleimide composites and preparation method | |
| CN102745994B (en) | Silicon carbide-carbon composite material and preparation method thereof | |
| CN106045380A (en) | Low-noise ceramic brake pad and preparation method thereof | |
| CN106893452A (en) | Nano rare earth modified epoxy anticorrosive paint and preparation method thereof | |
| CN103525003B (en) | Low-temperature plasma modified aluminum oxide enhanced phenolic resin and preparation method thereof | |
| WO2006077962A1 (en) | Thermosetting resin composite material and method for production thereof | |
| CN106753100B (en) | Inorganic nano particle hybrid phenolic resin adhesive and preparation method thereof | |
| CN101798443B (en) | Method for preparing nano ceric oxide/epoxy resin composite material | |
| CN105154724A (en) | Carbon nano tube reinforced aluminum-based composite material and preparation method thereof | |
| CN104109223B (en) | Aluminum-carbon refractory material hybrid modified phenolic resins and preparation method thereof | |
| JP2022518097A (en) | Method for Producing Carbon Nanoparticle Polymer Matrix Composite Material Using Electromagnetic Wave Irradiation | |
| CN102423672B (en) | Core-shell Al2O3/Al composite powder preparation process | |
| CN102675717A (en) | Modified nonmetallic reclaimed material of printed circuit board and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 Termination date: 20201017 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |