CN1876784A - Fluorinated lubricants - Google Patents
Fluorinated lubricants Download PDFInfo
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- CN1876784A CN1876784A CNA2006100927376A CN200610092737A CN1876784A CN 1876784 A CN1876784 A CN 1876784A CN A2006100927376 A CNA2006100927376 A CN A2006100927376A CN 200610092737 A CN200610092737 A CN 200610092737A CN 1876784 A CN1876784 A CN 1876784A
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- oil
- viscosity
- integer
- pour point
- perfluorinated polyether
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-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
- C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
- C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Abstract
Fluorinated lubricants comprising 'pour point depressant' additives of structure: X 1 -O (CF 2 O) n (CF 2 CF 2 O) m (CF 2 CF 2 CF 2 O) p (CF 2 CF 2 CF 2 CF 2 O) q -X 2 (I) wherein -X 1 , X 2 , have formula -(CF 2 ) z CF 3 wherein z is an integer from 0 to 3; n is an integer between 1 and 200; m is an integer between 0 and 200; p,q are integers between 0 and 10; (p+q)/(p+q+m+n) s 0.05; m/n s 0.7; the number average molecular weight of (I) is between 1,000 and 10,000.
Description
The present invention relates to reduce the fluorinated derivatives of lubricating oil pour point temperature.
Concrete, the present invention relates to the perfluorinated polyether based compound as reducing fluorinated oil, the additive that particularly has the fluorinated oil pour point temperature of perfluorinated polyether structure uses, and the lubricating oil composition that contains described additive.
Known in the existing technology, polyether oil uses as lubricating oil in a very wide temperature range, particularly is applied to require also can have good lubricating property under low-down temperature, for example in space flight and refrigeration industry.In these commercially available lubricating oil, mention the FOMBLIN that sells by Solvay SolexisS.p.A with perfluorinated polyether structure
, it in addition can be lower than in temperature under-80 ℃ and use as lubricating oil.
Known, no matter lubricating oil be fluorizated or not by fluorizated, the lower limit of Shi Yonging is relevant with their pour point temperature at low temperatures, if use below their pour point, owing to be difficult to make lubricating oil itself to be moved, then needs a lot of energy.In fact, in not by fluorizated lubricating oil,, crystallization takes place, and in fluorizated lubricating oil, for example perfluorinated polyether oil can be observed the unexpected rising of viscosity corresponding to pour point.
In order to reduce the pour point of lubricating oil, known method is to use " pour point depressant ".For example the nonfluorinated additive has been developed and has been applicable to hydrowax oil, mineral oil and oil.Examples of such additives is generally the hydrogenant polymkeric substance, can be miscible with lubricating oil, and when temperature reduces, can stop the lubricating oil crystallization and do not change the characteristic of lubricating oil, and then show the oilness of lubricating oil.The example of described additive is a polymethyl acrylic acid allylic alkylation ester, polyacrylic ester, phthalic ester.For example, describe among the patent application WO89/01507, when use comprises molecular weight 10,000-300, the polymethyl acrylic acid alkene ester between 000 scope can make the pour point of paraffin oil reduce to-35 ℃ approximately during as " pour point depressant " additive.
Yet, the nonfluorinated additive fluorinated lubricants for example the application in the perfluorinated polyether oil be infeasible because described additive and fluorinated lubricants unmixing.
In the fluorinated lubricants field, perfluorinated polyether oil especially, the pour point suppressant additive that can reduce pour point can not obtain on market.
Therefore, useful additive need satisfy following requirement:
-can reduce the pour point of perfluorination lubricating oil, perfluorinated polyether oil especially;
-can be dissolved in fluorinated oil, perfluorinated polyether oil especially;
-do not change the lubricating property of fluorinated lubricants basically, especially for perfluorinated polyether oil, viscosity for example, vaporization losses, chemical stability, viscosity index does not especially change viscosity index;
And then widen described fluorinated lubricants thermal rating at low temperatures, especially perfluorinated polyether lubricating oil.
The unexpected also surprised discovery of the applicant joins the pour point temperature that can reduce described perfluorinated polyether oil in the perfluorinated polyether oil with specific fluorochemical, and can solve above-mentioned technical problem simultaneously.
An object of the present invention is to have the compound effects fluorinated oil of following structural formula, particularly the purposes of perfluorinated polyether oil pour point depressant additive.
X
1-O(CF
2O)
n(CF
2CF
2O)
m(CF
2CF
2CF
2O)
p(CF
2CF
2CF
2CF
2O)
q-X
2 (I)
Wherein:
-multiple structural unit-CF
2O-,-CF
2CF
2O-,-CF
2CF
2CF
2O-,-CF
2CF
2CF
2CF
2O-is statistical distribution along structural chain
--X
1With-X
2Be the perfluoroalkyl last-of-chain group that is same to each other or different to each other, have structural formula-(CF
2)
ZCF
3, wherein z is from 0 to 3 integer;
-n is from 1 to 200 integer;
-m is from 0 to 200 integer;
-p, q is from 0 to 10 integer, is preferably from 0 to 5, more preferably from 0 to 1, more preferably 0,
And following supplementary condition are arranged:
-(p+q)/(p+qm+n) ratio is less than or equal to 0.05, also can equal 0, (p+q+m+n) is not 0;
-when n was not 0, the ratio of m/n was less than or equal to 0.7, preferably less than 0.5, was more preferably less than 0.35;
The scope from 1,000 to 10,000 of the number-average molecular weight of-compound (I), preferably from 2,000 to 8,000, more preferably from 2,400 to 5,000.
Additive of the present invention is passing through
19When F NMR analyzed, not showing wherein had the chlorine atom, and promptly the latter does not have basically.For compound with structural formula (I), by
19F NMR detects, and does not wherein also have the chlorine atom to exist substantially, means that promptly the amount of chlorine atom in the above-claimed cpd is lower than
19The threshold of sensitivity of F NMR analytical method.
Additive with structural formula (I) joins in the fluorinated oil, and especially the viscosity 20 ℃ the time is at 10-4, between the 000cSt, preferably at 30-2, between the 000cSt, and comprise in the perfluorinated polyether oil of one or more following repeated structural units :-CFXO-, wherein X is F or CF
3-CF
2CF
2O-,-(C
3F
6O)-,-CF
2CF
2CF
2O-,-CF
2CF
2CF
2CF
2O-, described structural unit is statistical distribution along structural framework.
Described perfluorinated polyether oil is preferably as follows kind: (1) E-O-(CF
2CF (CF
3) O)
M '(CFXO)
N '-E '
Wherein:
X is F or CF
3
E and E ' are same to each other or different to each other, and are selected from CF
3, C
2F
5Or C
3F
7, one or two above-mentioned end group
A F atom in the group can be replaced by Cl and/or H;
M ' and n ' are for making the integer of ratio between 20 to 1,000 of m '/n ', and n ' is not equal to 0;
This structural unit is statistical distribution along structural framework, and the viscosity of product is within above-mentioned scope.
These polymerizations can be passed through as GB 1,104, and the photoxidation of the perfluorination propylene described in 432 is pressed then as GB1, and the method described in 226,566 is carried out end group and transformed and obtain;
(2)C
3F
7O(CF(CF
3)CF
2O)
o′-D
Wherein:
D is-C
2F
5Or-C
3F
7, a F atom in one or two above-mentioned end group group can be replaced by Cl and/or H;
The value of o ' is the integer of viscosity within above-mentioned scope that makes product.
These polymkeric substance can be pressed as USP3 by the ion oligomerization and the use fluorine of perfluorination propylene oxide, and the method described in 242,218 is done further processing and prepared;
(3){C
3F
7O-(CF(CF
3)CF
2O)
p′-CF(CF
3)-}
2
Wherein:
P ' is for making the integer of viscosity within above-mentioned scope of product, one or two end group group C
3F
7In a F atom can be replaced by Cl and/or H.
These products can pass through the ion telomerization of perfluorination propylene oxide and press as USP 3,214, and the method described in 478 is done further photochemistry dimerization reaction and prepared;
(4)E-O-(CF
2CF(CF
3)O)
q′(C
2F
4O)
r′(CFX)
s′-E′
Wherein:
X is F or CF
3
E and E ' can be same to each other or different to each other as previously discussed;
Q ', r ' and s ' comprise 0 integer, and their value makes the viscosity of product within above-mentioned scope.
These polymkeric substance can pass through C
3F
6And CF
4The photooxidation reaction of mixture and use fluorine are pressed as USP3, and the method described in 665,041 is done further processing and prepared;
(5)E-O-(C
2F
4O)
t′(CF
2O)
u′-E′
Wherein:
E and E ' can be same to each other or different to each other as previously discussed;
T ' and u ' be for making the integer of ratio between 0.1 and 5 of t '/u ', the value of u ' be not equal to 0 and the viscosity that makes product within above-mentioned scope.
These polymkeric substance can pass through as USP 3,715, and the method described in 378 is carried out C
2F
4Photooxidation reaction and use fluorine by as USP 3,665, the method described in 041 is done further processing and is prepared;
(6)E-O-(CF
2CF
2CF
2O)
v′-E′
Wherein:
E and E ' can be same to each other or different to each other as previously discussed;
V ' is for making the number of viscosity within above-mentioned scope of product.
These polymkeric substance can prepare by the method described in EP 148,482;
(7)D-O-(CF
2CF
2O)
z′-D′
Wherein:
D and D ' can be same to each other or different to each other, and are selected from C
2F
5Or C
3F
7, a fluorine atom in one or two end group group can be replaced by Cl and/or H;
Z ' is for making the integer of viscosity within above-mentioned scope of product.
These polymkeric substance can pass through as USP 4,523, and the method described in 039 prepares;
(8)E
1-O(CF
2O)
n(CF
2CF
2O)
m-(CF
2CF
2CF
2O)
p(CF
2CF
2CF
2CF
2O)
q-E
2
Wherein:
E
1And E
2For perfluoroalkyl end group group, can be same to each other or different to each other, and have chemical formula-(CF
2)
zCF
3, wherein z is from 0 to 3 integer;
N, m, p, q are from 0 to 100 integer, and they each other can be identical or different, and their value be for can make oil viscosity within above-mentioned scope, and the ratio that can make m/n is between 2 to 20, and n is not equal to 0; (p+q)/(n+m+p+q) ratio is not 0 (n+m+p+q) between 0.05 to 0.2; The ratio of n/ (n+m+p+q) is not 0 (n+m+p+q) between 0.05 to 0.40.These polymkeric substance can pass through EP 1,454, and the method described in 938 prepares.Preferred perfluorinated polyether oil is (1) in the above-claimed cpd kind, (4), (5), (8) or their mixture, commercially available on the market as FOMBLIN by Solvay Solexis sale
And (2) in the above-claimed cpd, (6) also are operable.
Become benchmark with final group of products, the usage quantity of additive of the present invention is 0.1%-30% by weight, preferred 1%-20%, more preferably 5%-10%.
Another object of the present invention provides the lubricating oil composition that comprises (weight %) following component:
A) 70% to 99.9% at least a fluorinated oil by weight is preferably a kind of perfluorinated polyether oil, and its viscosity of 20 ℃ between the 000cSt, preferably at 30-2, between the 000cSt, and comprises one or more following multiple structural units at 10-4:
-CFXO-, wherein X is F or CF
3-CF
2CF
2O-,-(C
3F
6O)-,-CF
2CF
2CF
2O-,-CF
2CF
2CF
2CF
2O-, described structural unit is statistical distribution along structural framework; With
B) at least a additive of 0.1%-30% by weight with chemical formula (I).
In these compositions, the perfluorinated polyether oil mixt all can be used with the additive agent mixture with general formula (I).
Described composition especially preferably comprises a kind of additive and at least a kind (1) with chemical formula (I), the oil of (5); Described composition more preferably comprises the oil of 20 ℃ the kind (5) of viscosity between 30cSt-300cSt.
Lubricating oil composition of the present invention does not have the lubricating oil of additive to have lower pour point.
Pour point of the present invention is lower than-95 ℃ lubricating oil composition and especially is useful in the application of spationautics; Low pour point is being represented a kind of progress with respect to obtainable perfluorinated polyether oil on the market.
Oil compositions pour point temperature of the present invention is with respect to low at least 4 ℃ of any perfluorinated polyether lubricating oil pour point temperature that is wherein comprised, and reduces by 5% at least with comparing without any the pour point temperature of the oil of additive (can referring to Comparative Examples).
In addition, the additive with chemical formula (I) can be dissolved in the perfluorinated polyether oil fully, and lubricating oil composition of the present invention is transparent, and therefore, described lubricating oil composition is stable on thermodynamics.Thereby its distinctive advantage is not to be separated between the shelf lives.
Lubricating oil composition of the present invention can also comprise the additive that is usually used in the perfluorinated polyether oil, as rust-preventive agent, and anti-wear agent, oxidation inhibitor, thermo-stabilizer.
As previously described, the application of lubricating oil composition of the present invention, especially favourable being applicable to for example is applied to spationautics, refrigeration technology and the device that uses in the field that requires to have certain lubricity under low-down service temperature in low temperature and vacuum.
The applicant further finds that additive of the present invention except being liquid 20 ℃ the time and having the low vapour pressure, also shows high viscosity index and is lower than-90 ℃ pour point, preferably is lower than-95 ℃, more preferably less than-100 ℃.Therefore, described additive itself also can use as lubricating oil.
Further aim of the present invention is the use of compound (I) as low pour point lubricating oil.
Compound with chemical formula (I) for example can prepare by the following process that comprises the steps: a) peroxide perfluoropolyethers is synthetic, can obtain by one in following reaction reaction:
A1) photoxidation of tetrafluoroethylene (TFE), under the irradiation of ultraviolet, temperature is reacted in having the solvent liquid of following chemical formula and at reaction conditions between-40 ℃ to-100 ℃:
C
yF
(2y+2-x)H
x (II)
Wherein y is from 2 to 4 integer; X is integer 0 or 1;
Use element fluorine as chain-transfer agent, and use inert gas dilution;
Or
A2) oxidation of TFE can be used the radical initiator fluorine or have the inferior fluorochemical of following chemical formula:
R
fOF (III)
R
fFor having the perfluoroalkyl free radical of 1-3 carbon atom, reaction conditions is a temperature-40 ℃～-100 ℃, pressure 0～12 crust, and in inert solvent;
The preferred a2 that adopts) reaction;
B) under 150 ℃-250 ℃ temperature, the peroxidation product that obtains in the step a) is heat-treated, selectively, in the presence of the chain-transfer agent that is selected from time fluorochemical shown in element fluorine and one or more chemical formulas (III), carry out;
C) under 100 ℃-250 ℃ temperature, with element fluorine the polymkeric substance that obtains in the step b) is handled, perhaps handled with element fluorine under uviolizing, corresponding treatment temp is from-50 ℃-120 ℃.
Generally at step a1) in, the add-on of fluorine is to make the mol ratio of fluorine/tetrafluoroethylene 210
-2With 1.210
-3Between, preferably 1.210
-2With 1.710
-3Between, be 1/50 to 1/1,000 by volume with the ratio of inert gas dilution.
At step a1) in, used solvent is preferably following solvent: perfluorination propane (C
3F
8), a hydrogen five fluorinated ethanic (C
2F
5H) and 2-one hydrogen seven fluoridize propane (CF
3CFHCF
3), C
4F
9H is (as CF
3CFHCF
2CF
3, (CF
3)
3CH, HCF
2CF
2CF
2CF
3).
Step a1) employed solvent is liquid down at synthesis temperature (40 °--80 ℃) in, and can dissolve the peroxidation polymkeric substance, even can dissolve high-molecular weight peroxidation polymkeric substance, forms homogeneous phase solution.Because do not have the separation of peroxidation polymkeric substance, this has shown a marked improvement of the present invention.This makes described process be applied in the industrial possibility that becomes, and reason is can not take place owing to uncontrollable viscosity increases the obstruction that causes plant piping.Further, heat exchanger effectiveness is very high, has therefore avoided the uncontrollable degraded of peroxidation polymkeric substance.
Step a1) thus in the solvent that uses keep the high productivity except making reaction have high reaction kinetics, also keep and polymkeric substance in low peroxidation content, be lower than 4-5g active oxygen/100g product, avoid blast.
As previously mentioned, fluorine used step a1) must be used gas dilution.The general rare gas element of using is as using nitrogen or helium.Oxygen also can be used for doing thinner.In fact, when using not diluted fluorine, fluorine can produce uncontrollable local reaction and gas-phase decomposition product.For the polyreaction under the irradiation of UV ray, since reactor and optical system (ultraviolet lamp) fouling, the termination that the latter can induce reaction.In addition, in these cases, the increase that P.O. is out of control can be higher than the situation of 4-5g active oxygen/100g product, brings the danger of blast to system.Use after diluted, at step a1) in just show very high selectivity as the fluorine of chain-transfer agent, selection rate can reach 90%.Further, at step a1) in, fluorine reduce and basically eliminate the induction time of reaction, thereby avoided the use of reacting movable agent.
At step a2) in, wherein the oxidation of TFE is to carry out under the situation of not using UV-light, can use above-mentioned solvent, or chlorinated solvent.CF for example
2Cl
2, it should be noted that and selectively use and COF
2The mixture that forms.
At step a2) in, the molar ratio range of TFE/ chemical initiator is between 10-200, preferably at 40-120.
In step b),, can not use chain-transfer agent when molecular weight control not necessarily the time.For example, the viscosity that has served as oxidation products is lower than 5 at 20 ℃, during 000cSt above-mentioned situation can take place.
In step b), the flow rate of the inferior fluorochemical shown in normally used fluorine or the chemical formula (III) is from 110
-2-3moles.h/Kg polymkeric substance is preferably from 210
-2-2.
Step a in the process of the present invention and step b) can be carried out with discontinuous, semicontinuous or successive mode.
When the peroxidation concentration in the polymkeric substance did not exist substantially, step b) finished.This means that the P.O. value is equal to or less than employed Sensitivity of Analytical Method boundary (1ppm), described analytical procedure comprises the iodine that produces with thiosulfatimetry peroxidation polymkeric substance and sodium iodide reaction.Usually heat treatment period is 10 to 30 hours, and this depends on the P.O. value and the temperature of this step.
Step c) is carried out in discrete mode usually.By
19F NMR analyzes, when the sense end group (mainly is-OCF
2COF and-(threshold of sensitivity of this method: the 1meq/Kg polymkeric substance), reaction finishes OCOF) to be converted into the perfluoroalkyl end group.
In step c), the amount that adds fluorine normally makes its concentration in perfluorinated polyether consistent with the solubleness boundary of fluorine.Under the temperature of this step, the order of magnitude of its concentration is 10
-2Mole fluorine/rise polymkeric substance.
Can select the cut that obtains having given number-average molecular weight and regulation molecular weight distribution by distillage.
Provide some embodiments of the invention illustrative but indefiniteness below.
Embodiment
Characterizing method:
The mensuration of-pour point temperature:
According to the ASTMD97 method pour point temperature is measured.
Reporting the result is the mean value of 5 detected results.
The mensuration of-kinematic viscosity:
According to the ASTMD445 method kinematic viscosity is measured.
The mensuration of-viscosity index:
According to the ASTMD2270 method viscosity index is measured.The variation that viscosity index is higher and on the low side is owing to variation of temperature causes.
Embodiment 1
Get a kind of perfluorinated polyether oil of 95g kind (5), its trade name is Fomblin
Z25,20 ℃ kinematic viscosity is 255cSt, viscosity index is 356, pour point is-74 ℃, with the 5g number-average molecular weight be 2,467 and additive with chemical formula (I) be added in the perfluorinated polyether oil m/n=0.33 wherein, p+q/ (p+q+m+n)=0.016.
Press preceding method and measure, the composition pour point that obtains is-82 ℃.The viscosity index of described composition is 348.
Thus, the pour point of the lubricating oil composition that obtains ratio hangs down 8 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced about 11%.
What should mention is to add additive of the present invention (I) not change its lubricating quality in perfluorinated polyether oil, and the viscosity index of the lubricating oil composition that it obtained equates with base oil basically.
Embodiment 2
The additive that use has chemical formula (I) repeats embodiment 1 described step, but the number-average molecular weight of additive therefor is 3,777, m/n=0.31 and p+q/ (p+q+m+n)=0.016.
Press preceding method and measure, the mixture pour point that obtains is-80 ℃.
Thus, the pour point of the lubricating oil composition that obtains ratio hangs down 6 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced about 8%.
Embodiment 3 (comparative example)
The additive compound that use has chemical formula (I) repeats embodiment 1 described step, and the number-average molecular weight of additive therefor is 4,000, but m/n=0.8.
Press preceding method and measure, the mixture pour point that obtains is-76 ℃.
Thus, the pour point of the lubricating oil composition that obtains ratio only hangs down 3 ℃ as the pour point of the perfluorinated polyether oil of base oil, and so corresponding pour point temperature has reduced by 3%.
Embodiment 4
Get a kind of perfluorinated polyether oil of 90g kind (5), its trade name is Fomblin
Z03,20 ℃ kinematic viscosity is 30cSt, and pour point is-93 ℃, and the additive that 10g is had chemical formula (I) is added in the perfluorinated polyether oil, and its number-average molecular weight is 2,467, m/n=0.33 wherein, p+q/ (p+q+m+n)=0.016.
Press preceding method and measure, the mixture pour point that obtains is-102 ℃.
Thus, the pour point of the lubricating oil composition that obtains ratio hangs down 11 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced by 10%.
Embodiment 5
The additive that use has chemical formula (I) repeats embodiment 1 described step, and the number-average molecular weight of additive therefor is 3,777, m/n=0.31 and p+q/ (p+q+m+n)=0.016.
Press preceding method and measure, the mixture pour point that obtains is-99 ℃.
Thus, the pour point of the lubricating oil composition that present embodiment obtains ratio hangs down 6 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced by 6%.
Embodiment 6
The perfluorinated polyether oil that use has structure (6) repeats embodiment 1 described step as lubricating oil, and its trade name is Demnum
S-20 presses preceding method and measures, and its viscosity is 53cSt, and pour point is-75 ℃.
Press preceding method and measure, the mixture pour point that obtains is-79 ℃.
Thus, the pour point of the lubricating oil composition that present embodiment obtains ratio hangs down 4 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced by 6%.
Embodiment 7 (comparative example)
Repeat to implement 6 described steps, use have chemical formula (I) and number-average molecular weight be 4,000 compound as additive, but its m/n=0.8.
Press preceding method and measure, the mixture pour point that obtains is-75 ℃.
Thus, the pour point of the lubricating oil composition that obtains of present embodiment equals the pour point as the perfluorinated polyether oil of base oil.
Embodiment 8
The perfluorinated polyether oil that use has structure (6) repeats embodiment 4 described steps as lubricating oil, and its trade name is Demnum
S-200 presses preceding method and measures, and its viscosity is 500cSt, and pour point is-53 ℃.
Press preceding method and measure, the mixture pour point that obtains is-63 ℃.
Thus, the pour point of the lubricating oil composition that present embodiment obtains ratio hangs down 10 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced by 19%.
Embodiment 9
The perfluorinated polyether oil that use has structure (2) repeats embodiment 1 described step as base oil, and its trade name is Krytox
1506, to press preceding method and measure, its viscosity is 60cSt, pour point is-47 ℃.
Press preceding method and measure, the mixture pour point that obtains is-51 ℃.
Thus, the pour point of the lubricating oil composition that present embodiment obtains ratio hangs down 4 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced by 9%.
Embodiment 10
Repeat embodiment 9 described steps, but will change the composition of mixture, promptly use 90g oil and 10g additive.
Press preceding method and measure, the mixture pour point that obtains is-56 ℃.
Thus, the pour point of the lubricating oil composition that present embodiment obtains ratio hangs down 9 ℃ as the pour point of the perfluorinated polyether oil of base oil, and promptly corresponding pour point temperature has reduced by 19%.
Embodiment 11
The additive that uses among the embodiment 1 is characterized, obtains following rerum natura:
-20 ℃ viscosity: 13cSt;
--60 ℃ viscosity: 344cSt;
-viscosity index: 381;
-pour point :-111 ℃.
From top report data as can be seen, clearly, the compound itself with chemical formula (I) also can be used as lubricating oil, and especially being applied to needs to use lubricated oil condition under low-down temperature.
Table 1
| Embodiment | Oil | Additive | |||||
| Trade name | Pour point (PP) (℃) | %wt. oil | %wt. oil | Type | Composition pour point (PP) (℃) | PP reduces (in%) | |
| 1 | Fomblin Z 25 | -74 | 95 | 5 | (I) | -82 | 11 |
| 2 | Fomblin Z 25 | -74 | 95 | 5 | (I) | -80 | 8 |
| 3 (comparative examples) | Fomblin Z 25 | -74 | 95 | 5 | (1) m/n＞0.7 wherein | -76 | 3 |
| 4 | Fomblin Z 03 | -93 | 90 | 10 | Embodiment 1 | -102 | 10 |
| 5 | Fomblin Z 03 | -93 | 90 | 10 | Embodiment 2 | -99 | 6 |
| 6 | Demnum S20 | -75 | 95 | 5 | Embodiment 1 | -79 | 6 |
| 7 (comparative examples) | Demnum S20 | -75 | 95 | 5 | Embodiment 3 | -75 | 0 |
| 8 | Demnum S200 | -53 | 90 | 10 | Embodiment 1 | -63 | 19 |
| 9 | Krytox 1506 | -47 | 95 | 5 | Embodiment 1 | -51 | 9 |
| 10 | Krytox 1506 | -47 | 90 | 10 | Embodiment 1 | -56 | 19 |
Claims (11)
1. have the purposes of the compound of following structure as fluorinated oil " pour point depressant " additive:
X
1-O(CF
2O)
n(CF
2CF
2O)
m(CF
2CF
2CF
2O)
p(CF
2CF
2CF
2CF
2O)
q-X
2 (I)
Wherein:
-multiple structural unit-CF
2O-,-CF
2CF
2O-,-CF
2CF
2CF
2O-,-CF
2CF
2CF
2CF
2O-is statistical distribution along structural chain;
--X
1With-X
2Be the perfluoroalkyl last-of-chain group that is same to each other or different to each other, have structural formula
-(CF
2)
ZCF
3, wherein z is from 0 to 3 integer;
-n is from 1 to 200 integer;
-m is from 0 to 200 integer;
-p, q is from 0 to 10 integer, is preferably from 0 to 5, more preferably from 0 to 1, more preferably 0,
And following supplementary condition are arranged:
-(p+q)/(p+q+m+n) ratio is less than or equal to 0.05, also can equal 0, (p+q+m+n) is not 0;
-when n was not 0, the ratio of m/n was less than or equal to 0.7, preferably less than 0.5, was more preferably less than 0.35;
The number-average molecular weight of-compound (I) is 1,000-10, and between 000, preferably 2,000-8, between 000, more preferably 2,400-5 is between 000; By the compound shown in the 19F NMR assay determination chemical formula (I), wherein there is not the chlorine atom to exist basically.
2. application according to claim 1, viscosity was at 10-4, between the 000cSt when fluorinated oil wherein was 20 ℃, preferably at 30-2, perfluorinated polyether oil between the 000cSt, and comprise one or more following repeated structural units :-CFXO-, wherein X is F or CF
3-CF
2CF
2O-,-(C
3F
6O)-,-CF
2CF
2CF
2O-,-CF
2CF
2CF
2CF
2O-, described structural unit is statistical distribution along structural framework.
3. application according to claim 2, kind is descended in perfluorinated polyether grease separation wherein freely:
(1)E-O(CF
2CF(CF
3)O)
m′(CFXO)
n′-E′
Wherein:
X is F or CF
3
E and E ' are same to each other or different to each other, and are selected from CF
3, C
2F
5Or C
3F
7, a fluorine atom in one or two above-mentioned end group group can be replaced by Cl and/or H; M ' and n ' for the ratio that makes m '/n ' at 20-1, the integer between 000, n ' are not equal to 0; This structural unit is statistical distribution along structural framework, and the viscosity of product is within above-mentioned scope;
(2)C
3F
7O(CF(CF
3)CF
2O)
o′-D
Wherein:
D is-C
2F
5Or-C
3F
7, a F atom in one or two above-mentioned end group group can be replaced by Cl and/or H; The value of o ' is the integer of viscosity within above-mentioned scope that makes product;
(3){C
3F
7O-(CF(CF
3)CF
2O)
p′-CF(CF
3)-}
2
Wherein:
P ' is for making the integer of viscosity within above-mentioned scope of compound, one or two end group group C
3F
7In a F atom can be replaced by Cl and/or H;
(4)E-O-(CF
2CF(CF
3)O)
q′(C
2F
4O)
r′(CFX)
s′-E′
Wherein:
X is F or CF
3
E and E ' can be same to each other or different to each other as previously discussed; Q ', r ' and s ' comprise 0 integer, and their value makes the viscosity of product within above-mentioned scope;
(5)E-O-(C
2F
4O)
t′(CF
2O)
u′-E′
Wherein:
E and E ' can be same to each other or different to each other as previously discussed; T ' and u ' be for making the integer of ratio between 0.1 and 5 of t '/u ', the value of u ' be not equal to 0 and the viscosity that makes product within above-mentioned scope;
(6)E-O-(CF
2CF
2CF
2O)
v′-E′
Wherein:
E and E ' can be same to each other or different to each other as previously discussed;
V ' is for making the number of viscosity within above-mentioned scope of product.
(7)D-O-(CF
2CF
2O)
z’-D′
Wherein:
D and D ' can be same to each other or different to each other, and are selected from C
2F
5Or C
3F
7, a F atom in one or two end group group can be replaced by Cl and/or H; Z ' is for making the integer of viscosity within above-mentioned scope of product;
(8)E
1-O(CF
2O)
n(CF
2CF
2O)
m-(CF
2CF
2CF
2O)
p(CF
2CF
2CF
2CF
2O)
q-E
2
Wherein:
E
1And E
2For perfluoroalkyl end group group, be same to each other or different to each other, and have chemical formula-(CF
2)
zCF
3, wherein z is from 0 to 3 integer;
N, m, p, q are from 0 to 100 integer, and they are identical or different each other, and their value can make oil viscosity within above-mentioned scope, and the ratio that can make m/n is between 2-20, and n is not equal to 0; (p+q)/(n+m+p+q) ratio is not 0 (n+m+p+q) between 0.05-0.2; The ratio of n/ (n+m+p+q) is not 0 (n+m+p+q) between 0.05-0.40.
4. application according to claim 3, wherein perfluorinated polyether oil is kind (1), (4), (5), (8) or their mixture and kind (2) and (6).
5. according to the described application of claim 1-4, wherein the consumption of pour point depressant additive with the final composition be benchmark by weight from 0.1%-30%, preferred 1%-20%, more preferably 5%-10%.
6. according to the described application of claim 1-5, use therein is additive agent mixture and the perfluorinated polyether oil mixt with general formula (I).
7. lubricating oil composition comprises:
A) at least a fluorinated oil of 70%-99.9% by weight is preferably a kind of perfluorinated polyether oil, and its viscosity of 20 ℃ is at 10-4, between the 000cSt, preferably at 30-2, between the 000cSt, and comprise one or more following multiple structural units :-CFXO-, wherein X is F or CF
3-CF
2CF
2O-,-(C
3F
6O)-,-CF
2CF
2CF
2O-,-CF
2CF
2CF
2CF
2O-, described structural unit is statistical distribution along structural framework; With
B) at least a additive of 0.1%-30% by weight with chemical formula (I).
8. composition according to claim 7 comprises at least a additive and at least a kind (1) with chemical formula (I), the oil of (5); The oil of the kind (5) of preferred a kind of viscosity between 30cSt-300cSt.
9. according to the described lubricating oil composition of claim 7-8, comprise rust-preventive agent, anti-wear agent, oxidation inhibitor, suitable perfluorinated polyether oil thermo-stabilizer.
10. the compound in the claim 1 (I) is as the application with low pour point lubricating oil.
11. the perfluorinated polyether lubricating oil of claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2005A001081 | 2005-06-10 | ||
| IT001081A ITMI20051081A1 (en) | 2005-06-10 | 2005-06-10 | FLUORINE LUBRICANTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1876784A true CN1876784A (en) | 2006-12-13 |
Family
ID=36955987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100927376A Pending CN1876784A (en) | 2005-06-10 | 2006-06-09 | Fluorinated lubricants |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060281640A1 (en) |
| EP (1) | EP1731592A3 (en) |
| JP (1) | JP2006348292A (en) |
| CN (1) | CN1876784A (en) |
| IT (1) | ITMI20051081A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928634A (en) * | 2010-09-10 | 2010-12-29 | 航空工业总公司过滤与分离机械产品质量监督检测中心 | Method for purifying perfluoroalkylpolyether |
| CN103254975A (en) * | 2008-02-01 | 2013-08-21 | 优迈特株式会社 | Thermal decomposition ihibition method of fluorinated oils |
| CN105575408A (en) * | 2015-12-08 | 2016-05-11 | 衢州氟硅技术研究院 | Lubricating oil composition for magnetic disk |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20062308A1 (en) * | 2006-11-30 | 2008-06-01 | Solvay Solexis Spa | ADDITIVES FOR HALO-POLYMERS |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3242218A (en) * | 1961-03-29 | 1966-03-22 | Du Pont | Process for preparing fluorocarbon polyethers |
| DE1249247B (en) * | 1961-04-25 | 1967-09-07 | E. I. Du Pont De Nemours And Company, Wilmington, Del. (V. St. A.) | Process for the preparation of perfluoroolefin polyethers |
| DE1745169B2 (en) * | 1967-02-09 | 1977-04-21 | Montecatini Edison S.P.A., Mailand (Italien) | FLUORINATED LINEAR POLYAETERS AND THE PROCESS FOR THEIR PRODUCTION |
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
| US4523039A (en) * | 1980-04-11 | 1985-06-11 | The University Of Texas | Method for forming perfluorocarbon ethers |
| US5202501A (en) * | 1985-11-08 | 1993-04-13 | Exfluor Research Corporation | Perfluoropolyethers |
| US4827042A (en) * | 1985-11-08 | 1989-05-02 | Exfluor Research Corporation | Perfluoropolyethers |
| US5624713A (en) * | 1996-01-25 | 1997-04-29 | Zardoz Llc | Method of increasing lubricity of snow ski bases |
| AU1094200A (en) * | 1998-09-29 | 2000-04-17 | Loctite Corporation | Fluorinated oil-containing compositions |
-
2005
- 2005-06-10 IT IT001081A patent/ITMI20051081A1/en unknown
-
2006
- 2006-05-23 EP EP06010615A patent/EP1731592A3/en not_active Withdrawn
- 2006-06-08 US US11/448,670 patent/US20060281640A1/en not_active Abandoned
- 2006-06-09 CN CNA2006100927376A patent/CN1876784A/en active Pending
- 2006-06-09 JP JP2006161170A patent/JP2006348292A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254975A (en) * | 2008-02-01 | 2013-08-21 | 优迈特株式会社 | Thermal decomposition ihibition method of fluorinated oils |
| CN103254975B (en) * | 2008-02-01 | 2015-06-24 | 优迈特株式会社 | Thermal decomposition ihibition method of fluorinated oils |
| CN101928634A (en) * | 2010-09-10 | 2010-12-29 | 航空工业总公司过滤与分离机械产品质量监督检测中心 | Method for purifying perfluoroalkylpolyether |
| CN101928634B (en) * | 2010-09-10 | 2012-11-21 | 航空工业总公司过滤与分离机械产品质量监督检测中心 | Method for purifying perfluoroalkylpolyether |
| CN105575408A (en) * | 2015-12-08 | 2016-05-11 | 衢州氟硅技术研究院 | Lubricating oil composition for magnetic disk |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI20051081A1 (en) | 2006-12-11 |
| JP2006348292A (en) | 2006-12-28 |
| EP1731592A2 (en) | 2006-12-13 |
| US20060281640A1 (en) | 2006-12-14 |
| EP1731592A3 (en) | 2007-08-29 |
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