CN103160077B - Self-lubrication-type wear-resistant epoxy resin containing POSS and preparation method thereof - Google Patents
Self-lubrication-type wear-resistant epoxy resin containing POSS and preparation method thereof Download PDFInfo
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- CN103160077B CN103160077B CN201310044777.3A CN201310044777A CN103160077B CN 103160077 B CN103160077 B CN 103160077B CN 201310044777 A CN201310044777 A CN 201310044777A CN 103160077 B CN103160077 B CN 103160077B
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Abstract
The invention provides a self-lubrication-type wear-resistant epoxy resin containing POSS and a preparation method of the self-lubrication-type wear-resistant epoxy resin, and relates to a self-lubrication composite material and a preparation method of the self-lubrication composite material. A method of integration of assembling, polymerization and dispersion is adopted, firstly polymerizable silsesquioxane maleic acid macrogol ester (POSS-MA-PEG) can be synthesized and serves as emulsifying agents, and lubrication oil is wrapped up under the action of assembling to form nanoscale particles containing the lubrication oil; under the action of cross-linking agents, the structure of the nanoscale particles is stabilized, a function of slowly releasing the lubrication oil is achieved, and a self-lubrication effect is achieved; and ultimately the nanoscale particles, expoxy resin, curing agents, the cross-linking agents and silane coupling agents are uniformly mixed and solidified to form the self-lubrication-type wear-resistant epoxy resin containing the POSS. The dispersion problem of inorganic nanometer particles in the epoxy resin is solved, meanwhile due to rigidity and the cage structure of the POSS, the wear-resistant performance of the epoxy resin is greatly improved, and the friction coefficient of the epoxy resin is greatly reduced due to composite rolling particles of the lubrication oil and the POSS-MA-PEG.
Description
Technical field
The invention belongs to self-lubricating hybrid material field, relating to a kind of containing POSS self-lubricating type antiwear epoxy resin and preparation method thereof, is exactly that a kind of polymerisable POSS emulsifier lubricating oil that contains of utilization forms nano level " ball " to obtain the self-lubricating type antiwear epoxy resin with slow release lubricant effect.
Background technology
Epoxy resin, owing to having good thermotolerance, mechanical property and the adhesion property good to base material, obtains widespread use in fields such as sizing agent, seal gum, coating.But the epoxy resin after solidification, due to the restriction of three-dimensional net structure, causes its friction and wear behavior poor.Traditional method adopts fiber and micro inorganic particle polarity to fill, but due to filler and matrix phase capacitive poor, make troubles to processing; Again because slag is fallen in the easy efflorescence of product after solidification, thus affect use.In recent years, nanoscale inorganic particles comes into one's own gradually because of features such as its size are little, surface energy is high, addition is few in anti-friction wear-resistant application, but how to improve nano inoganic particle dispersiveness is in the base difficult problem always.
Polyhedral Oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) is the hybrid molecule of a cage-like shape structure, has super-hydrophobicity, large steric effect and nanoscale.Placed hope on by means of the variation of monomer structure and nano-grade size and constructed novel nanocomposite materials, effectively improved the thermal characteristics of matrix material, mechanical property, antioxidant property even optical property etc.
In the self-lubricating research field of epoxy resin, (the manufacture method of a kind of self-lubricating composite and self-lubricating composite mould such as Wang Yiqing, Chinese patent, publication number CN101463181A) by epoxy resin, nano-aluminium oxide powder or silicon dioxide powder, tungsten disulfide or molybdenumdisulphide, carbon fiber and coupling agent mixing, make self-lubricating resin based composites through ball milling, vacuum stripping process.(the epoxy resin solid lubrication coating material and preparation method thereof such as Guo Qiang, Chinese patent, publication number CN101717604A) disclose a kind of epoxy resin solid lubrication coating material containing finishing graphite oxide and preparation method thereof, overcome the problem of graphite solid lubricant bad dispersibility in resin solution, but the aesthetic measure of material appearance is good not, application is subject to a definite limitation.Lubricating oil capsule is added to inside epoxy resin by Zhang Mingqiu etc. (a kind of self-lubricating type epoxide resin material and preparation method thereof, Chinese patent, publication number CN101348600A), improves the oilness of material.But its lubricating oil capsule prepared is micron-sized, and not only stability is bad, and dispersed poor in base material, easily produce hole, hole, have a strong impact on the mechanical property of material.You Bo etc. (a kind of POSS/ epoxy nanometer hybrid material and preparation method thereof, Chinese patent, publication number CN101985513A) report a kind of high heat-resisting containing POSS hybrid material, but but do not have oilness.Zhang Junying etc. (a kind of epoxidation POSS its preparation method, Chinese patent, publication number CN102643433A) prepare a kind of environmentally friendly, resistant to elevated temperatures containing POSS silicone resin, but do not have self lubricity equally.
At present, have not been reported containing POSS self-lubricating type epoxide resin and preparation method thereof.
The method of integration that the present invention adopts " assembling-polymerization-dispersion ", nano level " ball " is obtained containing POSS emulsifier lubricating oil so that one is polymerisable, the functional group utilizing " ball " shell to enrich strengthens the affinity between epoxy resin-base, solves and is difficult to lubricating oil stable dispersion to the problem in macromolecular material.Meanwhile, the rigidity of POSS and cage structure can improve the wear resisting property of epoxy resin.In addition, the polyoxyethylene glycol in nano level " ball " shell contains abundant functional group, adds the affinity between epoxy resin-base, improves " ball " dispersiveness in the base; Causing polymerisable emulsifier polymerization will make ball have higher stability, only reliablely the lubricating oil of ball inside just can be made to discharge as the external force such as extruding, friction, and thus epoxy matrix can have the character of long-acting lubrication.
Summary of the invention
The object of the invention is to provide a kind of containing POSS self-lubricating type antiwear epoxy resin and preparation method thereof.
Described containing POSS self-lubricating type antiwear epoxy resin, be by one containing initiated polymerization after POSS emulsifier lubricating oil, form a kind of rock steady structure, subsequently together with epoxy resin, solidifying agent, silane coupling agent solidification preparation and obtaining.
Described polymerizable is synthesized via a step amidate action and a step esterification by aminopropyl POSS, maleic anhydride, polyoxyethylene glycol containing POSS emulsifying agent (being abbreviated as POSS-MA-PEG).
The molecular structure of described polymerizable POSS-MA-PEG is as follows:
Wherein, R is isobutyl-or phenyl, and n is 50 ~ 150.
The preparation method of described POSS-MA-PEG is as follows:
(1) be dissolved in toluene by aminopropyl POSS, maleic anhydride, react 24h at 90 DEG C after, separating-purifying obtains POSS-MA.POSS, maleic anhydride molar ratio are 1.01:1 ~ 1.05:1.
(2) be dissolved in toluene by POSS-MA, polyoxyethylene glycol, tosic acid, react 36h at 135 DEG C after, separating-purifying obtains POSS-MA-PEG.The molar ratio of POSS-MA, polyoxyethylene glycol is 1:1.01 ~ 1:1.05, and tosic acid feeds intake and accounts for 0.01 ~ 1% of POSS-MA and polyoxyethylene glycol total mass
Oil (60SN, 70SN, 100SN), silicone oil etc. based on described lubricating oil.
Described epoxy resin is commodity epoxy resin, the compound namely containing two or more epoxide group in molecule, as glycidyl ether, and glycidyl amine, glycidyl ester etc.; Wherein glycidyl ether has bisphenol A-type, bisphenol-f type and bisphenol S type etc.; Glycidyl amine has aniline glycidyl amine, diaminodiphenylmethane four glycidyl amine etc.; Glycidyl ester has 2-glycidyl to (neighbour) phthalic acid ester etc.
Solidifying agent be with described epoxy resin with the use of amine or anhydrides compound etc., amine is as quadrol, diethylenetriamine, mphenylenediamine etc.; Anhydrides is as Tetra hydro Phthalic anhydride, pyromellitic dianhydride, tetrahydrotoluene tetracarboxylic anhydride etc.
Described linking agent is the monomer with two and two or more double bond, as N,N methylene bis acrylamide, multicondensed ethylene glycol double methacrylate etc.
Described silane coupling agent adopts general formula to be Y (CH
2)
nsiX
3silane coupling agent, wherein, n=0 ~ 3; X is chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group etc., and Y is amino or epoxy group(ing).
Described POSS-MA-PEG, lubricating oil, epoxy resin, solidifying agent, linking agent, silane coupling agent form by weight percentage and are followed successively by 0.1 ~ 2%, 0.5 ~ 20%, 50 ~ 85%, 10 ~ 30%, 0.01 ~ 1%, 0.01 ~ 2%.
The described preparation method containing POSS self-lubricating type antiwear epoxy resin is as follows:
(1) POSS-MA-PEG is dissolved in acetone, adds lubricating oil, linking agent, be warming up to 60 ~ 80 DEG C of reaction 6 ~ 12h after stirring and emulsifying 1 ~ 6h and obtain nano level lubrication " ball ".
(2) epoxy resin, solidifying agent, silane coupling agent are joined in above-mentioned emulsion and be uniformly mixed, pour mould into, dry 1 ~ 2h at 50 ~ 60 DEG C, after being then warming up to 170 DEG C in 2h, namely heat preservation solidification 2 ~ 3h obtains containing POSS self-lubricating type antiwear epoxy resin.
The invention provides the technique of a kind of green, simple preparation self-lubricating epoxy resin, there is following characteristics:
(1) synthesized a kind of polymerisable emulsifying agent containing POSS, the method adopting " assembling-polymerization " to combine obtains nano level lubrication " ball ".
(2) POSS-MA-PEG, silane coupling agent, epoxy resin three synergy make " ball " stable and uniform disperse in the base.
(3) rigidity of POSS and cage structure improve the wear resisting property of epoxy resin further, reduce its frictional coefficient
(4) " ball " after Polymeric encapsulation has higher stability, only reliablely the lubricating oil of ball inside just can be made to discharge as the external force such as extruding, friction, makes material have the character of long-acting lubrication.
Attached caption
The scanning electron microscope (SEM) photograph of nanometer " ball " in Fig. 1 embodiment 1.
Fig. 2 nano level lubrication " ball " model schematic.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
(1) preparation of POSS-MA-PEG
By 5g POSS, 0.56g maleic anhydride and 40mL toluene evenly miscible, logical nitrogen, react 24h at 90 DEG C after, separating-purifying obtains POSS-MA; By 1gPOSS-MA, 4.10g PEG2000,0.015g tosic acid and 40mL toluene evenly miscible, logical nitrogen, react 36h at 135 DEG C after, separating-purifying obtains POSS-MA-PEG.
(2) containing the preparation of POSS self-lubricating type antiwear epoxy resin
0.1g POSS-MA-PEG is dissolved in 15mL acetone, adds 0.5g silicone oil 0.1g methylene-bisacrylamide, is warming up to the emulsion that 60 DEG C of reaction 8h obtain containing nano level " ball " after stirring 2h; Add 100g epoxy resin E-51,20g4,4 '-diaminodiphenylsulfone(DDS), 0.2g aminopropyl triethoxysilane coupling agent pour mould into after stirring; Dry 1h at 60 DEG C and remove acetone, be warming up to 170 DEG C of solidification 2h in 2h and namely obtain containing POSS self-lubricating type antiwear epoxy resin.
Gained nanometer " ball " is characterized by scanning electron microscope, and structure as shown in Figure 1; Model schematic as shown in Figure 2.The particle diameter of Fig. 1 display " ball " is about 50nm.Gained is detected according to GB by M-200 type wear testing machine containing the friction and wear behavior of POSS self-lubricating type antiwear epoxy resin, and recording frictional coefficient is 0.3823 ± 0.03, and specific wear rate is 52.6 ± 1.8(× 10
-6mm
3/ Nm).
Embodiment 2 ~ 8
With embodiment 1 technique, change feeding intake of silicone oil in (2) and be respectively 2g, 5g, 8g, 11g, 13g, 15g, 17g, result is as shown in table 1.
Table 1 is the result of embodiment 2 ~ 8.
Table 1
Claims (9)
1. one kind contains POSS self-lubricating type antiwear epoxy resin, comprise POSS-MA-PEG, lubricating oil, epoxy resin, solidifying agent, linking agent, silane coupling agent, be followed successively by POSS-MA-PEG0.1 ~ 2 part, lubricating oil 0.5 ~ 20 part, epoxy resin 50 ~ 85 parts, 10 ~ 30 parts, solidifying agent, linking agent 0.01 ~ 1 part, silane coupling agent 0.01 ~ 2 part by weight;
The molecular structure of described POSS-MA-PEG is as follows:
Wherein, R is isobutyl-or phenyl, and n is 50 ~ 150.
2. one according to claim 1 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that described POSS-MA-PEG is synthesized via a step amidate action and a step esterification by aminopropyl POSS, maleic anhydride, polyoxyethylene glycol.
3. one according to claim 1 and 2 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that the preparation method of described POSS-MA-PEG is as follows:
(1) be dissolved in toluene by aminopropyl POSS, maleic anhydride, react 24h at 90 DEG C after, separating-purifying obtains POSS-MA; POSS, maleic anhydride molar ratio are 1.01:1 ~ 1.05:1;
(2) be dissolved in toluene by POSS-MA, polyoxyethylene glycol, tosic acid, react 36h at 135 DEG C after, separating-purifying obtains POSS-MA-PEG; The molar ratio of POSS-MA, polyoxyethylene glycol is 1:1.01 ~ 1:1.05, and tosic acid feeds intake and accounts for 0.01 ~ 1% of POSS-MA and polyoxyethylene glycol total mass.
4. one according to claim 1 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that oil or silicone oil based on described lubricating oil.
5. one according to claim 1 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that described epoxy resin is commodity epoxy resin, the compound containing two or more epoxide group in molecule.
6. one according to claim 1 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that solidifying agent be with described epoxy resin with the use of amine or anhydrides compound.
7. one according to claim 1 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that described linking agent is the monomer with two and two or more double bond.
8. one according to claim 1 is containing POSS self-lubricating type antiwear epoxy resin, it is characterized in that described silane coupling agent adopts general formula to be Y (CH
2)
nsiX
3silane coupling agent, wherein, n=0 ~ 3; X is chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group, and Y is amino or epoxy group(ing).
9. a kind of preparation containing POSS self-lubricating type antiwear epoxy resin as claimed in claim 1, is characterized in that above-mentioned POSS-MA-PEG, lubricating oil, epoxy resin, solidifying agent, linking agent, silane coupling agent proportions raw material, and as follows:
(1) POSS-MA-PEG is dissolved in acetone, adds lubricating oil, linking agent, be warming up to 60 ~ 80 DEG C of reaction 6 ~ 12h after stirring and emulsifying 1 ~ 6h and obtain nano level lubrication " ball ";
(2) epoxy resin, solidifying agent, silane coupling agent are joined in above-mentioned emulsion and be uniformly mixed, pour mould into, dry 1 ~ 2h at 50 ~ 60 DEG C, after being then warming up to 170 DEG C in 2h, namely heat preservation solidification 2 ~ 3h obtains containing POSS self-lubricating type antiwear epoxy resin.
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| CN103450725B (en) * | 2013-08-13 | 2016-08-03 | 厦门大学 | A kind of Environment-friendlyfluorine/silicon-conheavyng fluorine/silicon-conheavyng heavyng anticorrosive epoxy resin paint and preparation method thereof |
| CN104292461B (en) * | 2014-09-16 | 2016-06-29 | 哈尔滨工业大学 | The preparation method of the PBO polymer that a kind of POSS is modified |
| CN105154175B (en) * | 2015-07-29 | 2018-01-09 | 广东月福汽车用品有限公司 | A kind of lubrication oil antiwear agent and preparation method thereof |
| CN105038441B (en) * | 2015-08-14 | 2017-08-15 | 上海祥水汽车零配件有限公司 | One pack system high abrasion, high adhesion force plastic paint |
| CN105131821B (en) * | 2015-09-24 | 2017-04-05 | 上海贻赛新材料科技有限公司 | A kind of aqueous polyurethane coating and preparation method thereof |
| CN105238505B (en) * | 2015-10-27 | 2018-03-16 | 广东月福汽车用品有限公司 | A kind of brakes lubricating grease and preparation method thereof |
| CN111001363B (en) * | 2019-11-15 | 2021-11-02 | 温州科技职业学院 | Preparation method of high-mechanical-strength nano microcapsule with insect-trapping function |
| CN117466599B (en) * | 2023-11-01 | 2024-05-07 | 宿迁华美新材料有限公司 | Corrosion-resistant precast concrete square pile |
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