CN103571567B - Cyclotriphosphazene ionic liquid used as lubricant and preparation method thereof - Google Patents

Cyclotriphosphazene ionic liquid used as lubricant and preparation method thereof Download PDF

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CN103571567B
CN103571567B CN201210265836.5A CN201210265836A CN103571567B CN 103571567 B CN103571567 B CN 103571567B CN 201210265836 A CN201210265836 A CN 201210265836A CN 103571567 B CN103571567 B CN 103571567B
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ionic liquid
monomethyl ether
phosphonitrile
ring
glycol monomethyl
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CN103571567A (en
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凡明锦
宋增红
周峰
刘维民
梁永民
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention discloses a cyclotriphosphazene ionic liquid used as a lubricant and a preparation method thereof. The ionic liquid is prepared by mixing the following components together: diglycol monomethyl ether, triglycol monomethyl ether, or tertglygol monomethyl ether derivatives of cyclotriphosphazene, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium trifluoromethanesulfonate or bis(trifluoromethane)sulfonimide lithium. The ionic liquid has a good chemical stability, thermal stability, and abrasion reducing and wear-resistant performance. The preparation method of the ionic liquid provided by the invention has the advantages of simple preparation process, low cost, excellent performance, and suitability for industrial application.

Description

As ring three phosphonitrile ionic liquid that lubricant uses and preparation method thereof
Technical field
The present invention relates to a kind of ring three phosphonitrile ionic liquid as lubricant use and preparation method thereof, this ion liquid lubricant has excellent anti-wear and wear-resistant performance.
Background technology
Ionic liquid is as a kind of efficient green solvent and environment-friendly catalyst in recent years, is subject to extensive concern (Welton, T. in fields such as organic synthesis, catalysis, electrochemistry; Wasserscheid, P. German:Wiley-VCH, 2002, 23.), its have nonflammable explosive, fusing point is low, volatility is extremely low and thermostability high, very identical with the performance desired by ideal lubricant, is novel lubricant (Ye, C. that a class has development prospect; Liu, W.; Chen, Y.; Yu, L. Chem. Commun. 2001, 21, 2244-2245.).Simultaneously, specific " designability " feature of ionic liquid, on the positively charged ion making us one or more functional group can be incorporated into ionic liquid or negatively charged ion, by ion liquid functionalization, the introducing of new functional group shows different physics-chem characteristics by making ionic liquid, and these characteristics directly may affect the tribological property of ionic liquid as lubricant.For the synthesis of functionalized ion liquid, preparation and tribology research, there is important Theory and applications be worth for designing and developing novel high-performance lubricant.The ionic liquid as lubricant that document has been reported is generally quaternary amine, quaternary phosphonium, pyridine, imidazoles are cationic ionic liquid, these ionic liquids all need to be obtained by steps such as alkylation, ion-exchange, separation, purifying, the synthesis step of its complexity, expensive cost and limit their application in tribological field to problems such as the corrodibility of substrate.Therefore, one of the ion liquid lubricant study hotspot remaining this field of design and preparation high-performance, low cost.
Summary of the invention
The object of the present invention is to provide a kind of ring three phosphonitrile ionic liquid as lubricant use and preparation method thereof.
The present invention has synthesized a kind of ring three phosphonitrile ionic liquid used as lubricant, and the molecular formula of this ionic liquid is [Li (P 3n 3(OR x) 6)] B; Wherein [Li (P 3n 3(OR x) 6)] +represent positively charged ion, x is 2,3 or 4; B -represent negatively charged ion tetrafluoroborate and (be called for short BF 4 -), hexafluoro-phosphate radical (be called for short PF 6 -), trifluoromethayl sulfonic acid root (be called for short CF 3sO 3 -) or two (trimethyl fluoride sulfonyl) imines root (abbreviation N (CF 3sO 2) 2 -or TFSI -); Described P 3n 3(OR x) 6represent P 3n 3(OR 2) 6, P 3n 3(OR 3) 6or P 3n 3(OR 4) 6, structural formula is
Be thick pale yellow shape transparent liquid under ionic liquid normal temperature provided by the present invention, initial pyrolyzation temperature, at about 230 DEG C, could decompose completely when temperature reaches nearly 500 DEG C.
A preparation method for ring three phosphonitrile ionic liquid, is characterized in that being prepared by following steps:
Synthesis sodium alkoxide: joined by sodium in the reactor of diethylene glycol monomethyl ether, triethylene glycol monomethyl ether or Tetraglycol 99 monomethyl ether, is heated to 115-125 DEG C and stirs until sodium reacts completely, obtain corresponding alcohol sodium solution under argon shield;
Synthesis P 3n 3(OR x) 6: take tetrahydrofuran (THF) as solvent, chlordene tripolyphosphazene is joined in alcohol sodium solution, stirred at ambient temperature reaction 10-12 hour, product washes with water after being dissolved in chloroform, obtains the diethylene glycol monomethyl ether of ring three phosphonitrile, triethylene glycol monomethyl ether or Tetraglycol 99 monomethyl ether derivative and (be called for short P after drying 3n 3(OR x) 6);
Prepare ring three phosphonitrile ionic liquid: P lithium salts and above step prepared 3n 3(OR x) 6mix and blend, until lithium salts all dissolves obtain ring three phosphonitrile ionic liquid.
In the process of synthesis sodium alkoxide, the mol ratio of diethylene glycol monomethyl ether, triethylene glycol monomethyl ether or Tetraglycol 99 monomethyl ether and sodium is 1:0.8-1.2.
At synthesis P 3n 3(OR x) 6process in, the mol ratio of chlordene tripolyphosphazene and sodium alkoxide is 1:5-7.
In the process of synthesis ring three phosphonitrile ionic liquid, with P 3n 3(OR x) 6the lithium salts of mixing is LiBF4 (LiBF 4), lithium hexafluoro phosphate (LiPF 6), trifluoromethayl sulfonic acid lithium (LiCF 3sO 3) or two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI).
In the process of synthesis ring three phosphonitrile ionic liquid, P 3n 3(OR x) 6be 1:5-7 with the mol ratio of lithium salts.
Oligopolymer ether compound (glymes) is stronger Lewis base, can with alkalimetal ion Li +composite formation Subacidity cation [Li (glyme)] +, [Li (glyme)] +again can further with weakly alkaline ion as TFSI -coordinate and form [Li (glyme)] TFSI ionic liquid (Tamura, T.; Yoshida, K.; Hachida, T. chem. Lett. 2010, 39, 753-755.).The present invention utilizes this principle exactly, forms homogeneous ion liquid lubricant by after the polyethers mix and blend of lithium salts and functionalization.These ionic liquids not only have higher chemical stability, thermostability and tribological property, and with conventional ion liquid phase than not needing ion-exchange in the preparation process of an in the end step, be separated, the step such as purifying, therefore cost significantly reduces.
The micro-vibration friction abrasion testing machine of SRV-IV adopting German optimol grease company to produce have rated the friction and wear behavior of invention ionic liquid, and to compare with general ionic liquid 1-methyl-3-base imidazoles two (trimethyl fluoride sulfonyl amine) (L-F102).Select load 500 N, temperature 200 DEG C, frequency 20 Hz, amplitude 1 mm, experimental period 30 min, experimentally tries as Si 3n 4ball, lower sample is W18Cr4V tool steel.This experimental result shows, the frictional coefficient of common ionic liquid is unstable, and resistance to abrasion is poor, and ring three phosphonitrile ionic liquid has very low and stable frictional coefficient and very excellent abrasion resistance.
Table 1: contrast ionic liquid L-F102 and synthesized ionic liquid at 500 N, the average friction coefficient under 200 DEG C of conditions and wear volume
Lubricant Average friction coefficient Wear volume/10 -5mm 3
L-F102 0.128 520.8
[Li(P 3N 3(OR x) 6)]B 0.096-0.100 119.2-124.3
Advantage of the present invention:
(1) involved in the present invention ionic liquid and conventional ion liquid phase ratio, do not need the preparation processes such as ion-exchange, separation, purifying in the synthesis of an in the end step, cost significantly reduces.
(2) involved in the present invention ionic liquid and conventional ion liquid phase ratio, have better friction stationarity and antiwear and friction reduction property.
Embodiment
For a better understanding of the present invention, be described by embodiment.
Embodiment 1:
[Li (P 3n 3(OR 2) 6] BF 4synthesis
By 9.61 g(0.08 mol) diethylene glycol monomethyl ether and 1.84 g(0.08 mol) sodium joins in 250 ml there-necked flasks, stirs until sodium reacts completely obtain alcohol sodium solution in about 115 DEG C under argon shield.With 120 ml tetrahydrofuran (THF)s for solvent, by 4.64 g(0.0133 mol) chlordene tripolyphosphazene joins in above-mentioned alcohol sodium solution, and stirred at ambient temperature reaction about 10 h, product is dissolved in chloroform after washing, drying obtains ring three phosphonitrile diethylene glycol monomethyl ether derivative P 3n 3(OR 2) 69.9 g(productive rates 87.2%).By P 3n 3(OR 2) 6with the LiBF of 6 times of molar weights 4mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 2) 6] BF 4.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.098 and 121.8 × 10 -5mm 3.
Embodiment 2:
[Li (P 3n 3(OR 3) 6] BF 4synthesis
By 16.43 g(0.1 mol) triethylene glycol monomethyl ether and 2.3 g(0.1 mol) sodium joins in 250 ml there-necked flasks, stirs until sodium reacts completely obtain alcohol sodium solution in about 120 DEG C under argon shield.With 150 ml tetrahydrofuran (THF)s for solvent, by 5.8 g(0.0166 mol) chlordene tripolyphosphazene joins in above-mentioned alcohol sodium solution, and stirred at ambient temperature reaction about 11 h, product is dissolved in chloroform after washing, drying obtains ring three phosphonitrile triethylene glycol monomethyl ether derivative P 3n 3(OR 3) 616.13 g(productive rates 86.8%).By P 3n 3(OR 3) 6with the LiBF of 6 times of molar weights 4mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 3) 6)] BF 4.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.097 and 120.5 × 10 -5mm 3.
Embodiment 3:
[Li (P 3n 3(OR 4) 6] BF 4synthesis
By 12.5 g(0.06 mol) Tetraglycol 99 monomethyl ether and 1.38 g(0.06 mol) sodium joins in 250 ml there-necked flasks, stirs until sodium reacts completely obtain alcohol sodium solution in about 125 DEG C under argon shield.With 100 ml tetrahydrofuran (THF)s for solvent, by 3.48 g(0.01 mol) chlordene tripolyphosphazene joins in above-mentioned alcohol sodium solution, and stirred at ambient temperature reaction about 12 h, product is dissolved in chloroform after washing, drying obtains ring three phosphonitrile Tetraglycol 99 monomethyl ether derivative P 3n 3(OR 4) 611.6 g(productive rates 83.9%).By P 3n 3(OR 4) 6with the LiBF of 6 times of molar weights 4mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 4) 6] BF 4.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.099 and 113.5 × 10 -5mm 3.
Embodiment 4:
[Li (P 3n 3(OR 2) 6] PF 6synthesis
Ring three phosphonitrile diethylene glycol monomethyl ether derivative P 3n 3(OR 2) 6preparation with embodiment 1.By P 3n 3(OR 2) 6with the LiPF of 6 times of molar weights 6mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 2) 6] PF 6.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.098 and 120.8 × 10 -5mm 3.
Embodiment 5:
[Li (P 3n 3(OR 3) 6)] PF 6synthesis
Ring three phosphonitrile triethylene glycol monomethyl ether derivative P 3n 3(OR 3) 6preparation with embodiment 2.By P 3n 3(OR 3) 6with the LiPF of 6 times of molar weights 6mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 3) 6)] PF 6.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.099 and 121.9 × 10 -5mm 3.
Embodiment 6:
[Li (P 3n 3(OR 4) 6] PF 6synthesis
Ring three phosphonitrile Tetraglycol 99 monomethyl ether derivative P 3n 3(OR 4) 6preparation with embodiment 3.By P 3n 3(OR 4) 6with the LiPF of 6 times of molar weights 6mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 4) 6] PF 6.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.096 and 120.3 × 10 -5mm 3.
Embodiment 7:
[Li (P 3n 3(OR 2) 6] CF 3sO 3synthesis
Ring three phosphonitrile diethylene glycol monomethyl ether derivative P 3n 3(OR 2) 6preparation with embodiment 1.By P 3n 3(OR 2) 6with the LiCF of 6 times of molar weights 3sO 3mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 2) 6] CF 3sO 3.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.10 and 123.8 × 10 -5mm 3.
Embodiment 8
[Li (P 3n 3(OR 3) 6] CF 3sO 3synthesis
Ring three phosphonitrile triethylene glycol monomethyl ether derivative P 3n 3(OR 3) 6preparation with embodiment 2.By P 3n 3(OR 3) 6with the LiCF of 6 times of molar weights 3sO 3mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 3) 6)] CF 3sO 3.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.099 and 122.7 × 10 -5mm 3.
Embodiment 9:
[Li (P 3n 3(OR 4) 6] CF 3sO 3synthesis
Ring three phosphonitrile Tetraglycol 99 monomethyl ether derivative P 3n 3(OR 4) 6preparation with embodiment 3.By P 3n 3(OR 4) 6with the LiCF of 6 times of molar weights 3sO 3mixing, stirs until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 4) 6] CF 3sO 3.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.10 and 124.3 × 10 -5mm 3.
Embodiment 10:
[Li (P 3n 3(OR 2) 6] synthesis of TFSI
Ring three phosphonitrile diethylene glycol monomethyl ether derivative P 3n 3(OR 2) 6preparation with embodiment 1.By P 3n 3(OR 2) 6mix with the LiTFSI of 6 times of molar weights, stir until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 2) 6] TFSI.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.97 and 119.8 × 10 -5mm 3.
Embodiment 11:
[Li (P 3n 3(OR 3) 6] synthesis of TFSI
Ring three phosphonitrile triethylene glycol monomethyl ether derivative P 3n 3(OR 3) 6preparation with embodiment 2.By P 3n 3(OR 3) 6mix with the LiTFSI of 6 times of molar weights, stir until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 3) 6)] TFSI.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.096 and 119.2 × 10 -5mm 3.
Embodiment 12:
[Li (P 3n 3(OR 4) 6] synthesis of TFSI
Ring three phosphonitrile Tetraglycol 99 monomethyl ether derivative P 3n 3(OR 4) 6preparation with embodiment 3.By P 3n 3(OR 4) 6mix with the LiTFSI of 6 times of molar weights, stir until form homogeneous ion liquid lubricant [Li (P 3n 3(OR 4) 6] TFSI.It is at 500 N, and the average friction coefficient under 200 DEG C of conditions and wear volume are respectively 0.097 and 119.7 × 10 -5mm 3.

Claims (5)

1., as the ring three phosphonitrile ionic liquid that lubricant uses, the molecular formula of this ionic liquid is [Li (P 3n 3(OR x) 6)] B; Wherein [Li (P 3n 3(OR x) 6)] +represent positively charged ion, x is 2,3 or 4; B -represent negatively charged ion tetrafluoroborate, hexafluoro-phosphate radical, trifluoromethayl sulfonic acid root or two (trimethyl fluoride sulfonyl) imines root; Described P 3n 3(OR x) 6represent P 3n 3(OR 2) 6, P 3n 3(OR 3) 6or P 3n 3(OR 4) 6, structural formula is
; Described ring three phosphonitrile ionic liquid is prepared by following steps:
Synthesis sodium alkoxide: joined by sodium in the reactor of diethylene glycol monomethyl ether, triethylene glycol monomethyl ether or Tetraglycol 99 monomethyl ether, is heated to 115-125 DEG C and stirs until sodium reacts completely, obtain corresponding alcohol sodium solution under argon shield;
Synthesis P 3n 3(OR x) 6: take tetrahydrofuran (THF) as solvent, chlordene tripolyphosphazene is joined in alcohol sodium solution, stirred at ambient temperature reaction 10-12 hour, product washes with water after being dissolved in chloroform, obtains the diethylene glycol monomethyl ether of ring three phosphonitrile, triethylene glycol monomethyl ether or Tetraglycol 99 monomethyl ether derivative after drying;
Prepare ring three phosphonitrile ionic liquid: P lithium salts and above step prepared 3n 3(OR x) 6mix and blend, until lithium salts all dissolves obtain ring three phosphonitrile ionic liquid.
2.2 .ionic liquid as claimed in claim 1, it is characterized in that synthesizing in the process of sodium alkoxide, the mol ratio of diethylene glycol monomethyl ether, triethylene glycol monomethyl ether or Tetraglycol 99 monomethyl ether and sodium is 1:0.8-1.2.
3.3 .ionic liquid as claimed in claim 1, is characterized in that synthesizing P 3n 3(OR x) 6process in, the mol ratio of chlordene tripolyphosphazene and sodium alkoxide is 1:5-7.
4.4 .ionic liquid as claimed in claim 1, is characterized in that synthesizing in the process of ring three phosphonitrile ionic liquid, with P 3n 3(OR x) 6the lithium salts of mixing is LiBF4, lithium hexafluoro phosphate, trifluoromethayl sulfonic acid lithium or two (trimethyl fluoride sulfonyl) imine lithium.
5.5 .ionic liquid as claimed in claim 1, is characterized in that synthesizing in the process of ring three phosphonitrile ionic liquid, P 3n 3(OR x) 6be 1:5-7 with the mol ratio of lithium salts.
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CN1782043A (en) * 2004-11-30 2006-06-07 中国科学院兰州化学物理研究所 Ion liquid lubricant

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