CN101864041A - Liquid rubber surface modifier, surface modified nano-AlN and application thereof - Google Patents
Liquid rubber surface modifier, surface modified nano-AlN and application thereof Download PDFInfo
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- CN101864041A CN101864041A CN201010165223A CN201010165223A CN101864041A CN 101864041 A CN101864041 A CN 101864041A CN 201010165223 A CN201010165223 A CN 201010165223A CN 201010165223 A CN201010165223 A CN 201010165223A CN 101864041 A CN101864041 A CN 101864041A
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- aln
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- lubricating oil
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Abstract
The invention discloses a liquid rubber surface modifier. The liquid rubber surface modifier is a graft copolymer in which a maleic anhydride side group is introduced into a main chain of liquid rubber polybutadiene. The graft copolymer has a chemical formula, wherein m and n represent polymerization degrees; and the number-average molecular weight of the modifier is less than or equal to 10<4>. Surface modified nano-AlN is obtained by performing coating and modification treatment on nano-AlN powder particles by using the modifier. The lubricating property of lubricating oil can be improved effectively by adding the surface modified nano-AlN powder serving as the modifier of the lubricating oil into the lubricating oil.
Description
One, technical field
The present invention relates to a kind of large molecule surface modifier that is used for the nano powder surface modification, exactly is a kind of purposes that is used for the fluid rubber surface-modifying agent and the surface modification A1N of nanometer AlN powder surface modification.
Two, technical background
Ceramic nano particulate specific surface area is very big, the surface energy height, be in non-thermodynamics stable state, micron-particle has very strong activity, this makes them in use be easy to reunite together, and forming the larger-size coacervate have some weak linkage interfaces, this influences one of the major technique bottleneck of the practical application of micron-particle just.Therefore, in preparation and application process, need to carry out modification, with minimizing or stop its reunion to the surface of nanoparticle.
Pottery such as nitride or carbide is received and is had some reactive groups that can react on the micro-powder surface (as ,-NH
2,-OH ,-NH-etc.) can with-Cl (chloro) ,-SH (sulfydryl) ,-NCO (isocyanate group) ,-COCl (acid chloride group) ,-Li (active lithium end group) ,-chemical reaction takes place in COOH functional groups such as (carboxyls).This receives the micro-powder surface to pottery, and to carry out coating modification be very favourable.
At present, a lot of to nano powder modified method, as surface chemistry coating or graft modification, physical method modification, mechanochemical modification, energetic ray modification etc., the maximum of usefulness mainly are that surface chemistry coats or graft modification.Practice shows, macromole (polymkeric substance) properties-correcting agent is to the modification of nano powder surface coating decoration, and the effect of build bridge between itself and polymeric matrix (coupling) is better than small molecules properties-correcting agent.In recent years, development about large molecule surface modifier is very rapid, become important research project in the surface-modifying agent field, the large molecule surface modifier of particularly a large amount of novel structures, superior performance is designed synthetic and comes into operation, and has greatly promoted carrying out of correlative study work.
To possess following three conditions to receiving the molecules surfactant that the micro-powder particle surface carries out coating modification: (a) anchoring group of large molecule surface modifier with receive micro-powder particulate surface active groups and can form firm chemical bond and combine; (b) large molecule surface modifier is the solvation layer at particle surface energy formation tectum more complete, that adequate thickness is arranged, to overcome the reunion of receiving magnetism between micron particle and causing; (c) polarity of the solvation segment of large molecule surface modifier and be modified macromolecular material and material will similar or three-dimensional solubility parameters close or interaction parameter have good consistency.
Fluid rubber is that a kind of relative molecular mass is below 10000
Thick flowable liquids, belong to flexible oligopolymer.At present, in all solid rubber kinds corresponding liquid rubber is arranged nearly all, its kind is also more numerous and diverse, can call first-generation fluid rubber to fluid rubber not on the whole, as Liquid Ethylene Propylene Methylene (LEPDM), liquid polybutadiene rubber (LPB), liquid polyisoprene rubber (LIR) etc. with active end group or side group; The fluid rubber of band active end group or band active lateral group then belongs to s-generation fluid rubber, as end carboxyl liquid divinyl rubber (CTPB), terminal hydroxy liquid divinyl rubber (HTPB), end bromo liquid divinyl rubber (BTPB), liquid carboxyl (side group) butadiene-acrylonitrile rubber etc.
Three, summary of the invention
The present invention is intended to provide for modifying lubricating oil the nano aluminum nitride (A1N) of a kind of surface coating modification (being surface modification), and technical problem to be solved is to select suitable large molecule surface modifier.
Thinking of the present invention is to select a suitable kind in first-generation fluid rubber, introduces active lateral group as anchoring group on its main chain by the grafting means, realizes the coating modification to nano-AlN.
Technical scheme of the present invention is to go up grafted with maleic anhydride (maleic anhydride MAH) at fluid rubber polybutadiene rubber (LPB), promptly the graft copolymer of introducing the activity anhydride side group on the main chain of LPB is as fluid rubber surface-modifying agent (MAH-g-LPB), and this surface-modifying agent has following chemical formula:
M, n are the polymerization degree in the formula, require to make the modifier molecules amount to satisfy
The preparation method of this surface-modifying agent is a raw material with MAH and LPB, free radical initiation grafting copolymerization when 85～95 ℃ of temperature in xylene solvent and under the nitrogen protection.
The alleged surface-modified nano A1N of the present invention carries out coating modification with this surface-modifying agent MAH-g-LPB to nano-AlN powder granule surface to handle the nano-AlN powder that obtains in xylene solvent and under the nitrogen protection, the mass ratio of A1N and MAH-g-LPB is 100: 10～15.
Nanometer AlN passes through surface coating modification, MAH is as the hydroxyl isoreactivity group generation chemical bonding on anchoring section and AlN surface, LPB forms the complete solvated layer that adequate thickness is arranged as the solvation segment on the AlN surface, both prevented the reunion of nanometer AlN particulate, with various lubricating oil good consistency had been arranged again.
To be exactly surface-modified nano AlN powder add in the lubricating oil to improve lubricity as the properties-correcting agent of lubricating oil the purposes of the surface-modified nano AlN that the present invention is alleged, in other words in preparation lubricating oil/nano-AlN matrix material as the application of properties-correcting agent.The addition of properties-correcting agent is 0.2～0.5wt% of quality of lubrication oil.
Four, description of drawings
Fig. 1 is the MAH-g-LPB infared spectrum.
Fig. 2 is before and after the LPB grafting
1The H-NMR nuclear magnetic spectrum is before a is grafting, after b is grafting.
Fig. 3 is a nanometer AlN diameter of particle distribution plan, (a) for before the modification, (b) for after the modification.
Fig. 4 is a nanometer AlN transmission electron microscope picture, a
1, a
2Before modification, b
1, b
2After modification.
Fig. 5 is a lubrication friction surface topography light micrograph, and a1, a2 are lubricating oil environment (before the modification), and b1, b2 are lubricating oil/nano-AlN (0.2wt%) environment (after the modification).
Five, embodiment
Non-limiting examples is described below:
1, MAH-g-LPB's is synthetic
Under the nitrogen protection condition; in three mouthfuls of round-bottomed flasks; add a certain amount of MAH, LPB, dimethylbenzene successively; treat that it fully dissolves; and with water-bath rise to be 90 ℃ after, drip the xylene solution of quantitative initiator B PO, anti-gelation agent Acetanilide gradually, dropwise; reacted 3～5 hours, and made the xylene solution of graft product.In reaction solution, add quantitative methyl alcohol, make the graft copolymer precipitation.Throw out, extracts with Virahol in apparatus,Soxhlet's to constant weight then through washing, vacuum-drying, is dried to constant weight, obtains the very big light yellow translucent solid of viscosity.
More than each quality of material ratio is in the reaction: MAH: LPB: initiator: anti-gelation agent=2～4: 10: 0.1～2: 0.03.
The infrared spectra of product is seen Fig. 1.Product is at 1780cm
-1, 1830cm
-1There is the intensive absorption peak at two places, and therefore these two charateristic avsorption bands that the peak is MAH illustrate that maleic anhydride successfully is grafted in the polyhutadiene molecular chain.
A in the comparison diagram 2 figure and b scheme, and two keys peak of δ 4.9～5.3ppm correspondence is corresponding with δ 1.25ppm-CH
2-absorption peak, the ratio of both integration height is constant substantially, illustrates that graft reaction is not or not two keys place.The tertiary carbon hydrogen of δ 1.6ppm correspondence and δ 7.1ppm corresponding A r-CH2-/Ar-CH＜absorption peak obviously weaken, illustrate to occur on the tertiary carbon atom; But do not see the resonance absorbing peak of MAH correspondence among the MAH-g-LPB on figure (b), this is that the absorption peak that should be the MAH correspondence is positioned at the 7.3ppm place, and is just in time overlapping with the Ar-H absorption peak.
2, MAH-g-LPB is to the coating modification of nanometer AlN
Take by weighing certain amount of nano AlN and put into there-necked flask, add an amount of dispersion agent dimethylbenzene, logical nitrogen protection adds the MAH-g-LPB of nano-powder 10～15% weight again, 60～70 ℃ of following high-speed stirring after 2～5 hours, and refrigerated separation.Make solvent with dimethylbenzene, extract 72h, separate the back and in 50 ℃ of baking ovens, more than the vacuum-drying 10h, after 100 mesh sieves, promptly get active nano AlN, i.e. the AlN of MAH-g-LPB coating modification behind the taking-up ball milling.
Nanometer AlN powder after the modification is carried out particle size analysis, contact angle analysis and transmissioning electric mirror test.
(1) Fig. 3 is seen in particle size analysis
The particle diameter of nano-powder becomes the 42nm (see figure 3) by original 169nm after the modification, the anhydride group in the properties-correcting agent and the group combinations such as hydroxyl of nano powder surface are described, form new chemical bond, broken the reactive force between the original nano-powder, effectively stoped its reunion.
(2) contact angle analysis
Utilize surface tension instrument to measure and handle the contact angle of front and back nanometer AlN at water, ethylene glycol, and nanometer AlN surface free energy before and after the computing: 12.72 ° (in the water) and 61.19 ° (in ethylene glycol) of nanometer AlN powder contact angle before by modification is changed to 75.20 ° (in water) and 45.49 ° (in ethylene glycol), and surface energy is by 325.08J/M
2Be reduced to 38.87J/M
2, showing that handling back nanometer AlN powder surface wetting ability reduces, lipophilicity increases, and can better be dispersed in the lubricating oil.
Nanometer AlN powder contact angle and surface free energy analysis before and after table 1. modification
(3) transmissioning electric mirror test is seen Fig. 4
Fig. 4 schemes a for the transmission electron microscope (TEM) that large molecule surface modifier modified Nano AlN is dispersed in the alcohol solvent
1, a
2Be unmodified nanometer AlN, b
1, b
2It is the TEM photo that nanometer AlN after the modification amplifies 20,000 times and 100,000 times respectively.As can be seen, the mean particle size of the AlN after the modification in ethanol reduces from picture, the dispersed raising, and nanometer powder has tangible agglomeration before handling, and the nanometer powder after handling is uniformly dispersed in ethanol, agglomeration obviously reduces.
3, the nanometer AlN after the modification prepares lubricating oil/nano-AlN matrix material
Select commercially available brand lubricating oil for use, adopt intermittent type instantaneous pressure turbulent shear dispersing apparatus to prepare lubricating oil/nano-AlN matrix material, the adding proportion of active A lN is 0.2～0.5 (wt%) in the lubricating oil.
The lubricating oil matrix material has been carried out performance tests such as anti-extreme pressure energy, metallographic microanalysis.
(1) extreme pressure property test
The supporting capacity test of lubricating oil is according to the GB3142-82 regulation, at the last non seizure load (P of four-ball wear test aircraft measurements lubricating oil
B).The result is as shown in table 2, as can be seen Zhi Bei interpolation nanometer AlN lubricating oil have good and stable self-lubricating property, can well improve the supporting capacity of lubricating oil, extreme pressure value maximum can rise to 1396N from the 1000N of lubricating oil.
Table 2. lubricating oil/nano-AlN matrix material extreme pressure value (P
B, N)
(2) Metal Ball friction surface metallographic microanalysis
Fig. 5 is the lubrication friction surface optical displaing micro picture of Metal Ball, wherein a
1, a
2Be the lubricating oil environment; b
1, b
2Be lubricating oil/nano-AlN environment.As can be seen, figure a
1, a
2With respect to figure b
1, b
2, the friction surface cut is many and dark on the Metal Ball surface, illustrated that nanometer AlN oil film covers the Metal Ball surface after, play good antiwear and reducing friction effect, reduced the frictional coefficient of lubricating oil, to the lubricity of lubricating oil, the raising of supporting capacity plays an important role.
Claims (3)
1. fluid rubber surface-modifying agent is characterized in that: this properties-correcting agent is the graft copolymer of introducing the MALEIC ANHYDRIDE side group on fluid rubber polyhutadiene main chain, and following chemical formula is arranged
M, n are the polymerization degree in the formula, require to make the modifier molecules amount to satisfy
2. surface-modified nano aluminium nitride, it is characterized in that: by the described fluid rubber surface-modifying agent of claim 1 coating modification is carried out on nano aluminum nitride powder granule surface and handled the nano aluminum nitride powder that obtains, the mass ratio of aluminium nitride and properties-correcting agent is 100: 10～15.
3. the purposes of a surface-modified nano aluminium nitride is characterized in that: the surface-modified nano aluminium nitride in preparation lubricating oil/nano-AlN matrix material as the application of properties-correcting agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8242219B1 (en) | 2012-02-21 | 2012-08-14 | King Fahd University Of Petroleum And Minerals | Method of making polyolefin nanocomposites |
| CN105219495A (en) * | 2015-10-13 | 2016-01-06 | 惠州市中壳润滑油有限公司 | A kind of high-effect wear-resistant energy-saving lubricant oil and preparation method thereof |
| CN114752008A (en) * | 2022-05-20 | 2022-07-15 | 黄河三角洲京博化工研究院有限公司 | Method for preparing maleic anhydride high-vinyl liquid polybutadiene by using bulk method |
-
2010
- 2010-04-30 CN CN201010165223A patent/CN101864041A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8242219B1 (en) | 2012-02-21 | 2012-08-14 | King Fahd University Of Petroleum And Minerals | Method of making polyolefin nanocomposites |
| CN105219495A (en) * | 2015-10-13 | 2016-01-06 | 惠州市中壳润滑油有限公司 | A kind of high-effect wear-resistant energy-saving lubricant oil and preparation method thereof |
| CN114752008A (en) * | 2022-05-20 | 2022-07-15 | 黄河三角洲京博化工研究院有限公司 | Method for preparing maleic anhydride high-vinyl liquid polybutadiene by using bulk method |
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Application publication date: 20101020 |