Halogen-containing synthetic base oils, and preparation method and use thereof

Abstract

The present invention provides a class of halogen-containing synthetic base oils, and preparation method and use thereof. The synthetic base oils have introduced with halogen, especially fluorine, wherein the dipole motion of the halogen groups results in dipole interaction between the dipoles of other components and the base oil molecules of dipole-dipole and dipole-induced halogen (especially fluorine), and the interaction force is stronger and more localized than the dispersion force between the molecules of pure hydrocarbon synthetic oils, and thus the performance of the base oils is directly affected. It solved the problem of oil solubility of pure hydrocarbon synthetic oils, and also improved the properties of oxidation resistance and thermal stability.

Claims

1. A halogen-containing synthetic base oil, characterized in that the base oil contains FF-PAO and/or F-PAO, which are prepared from PAO as follows: ##STR00007## wherein: PAO is ##STR00008## molecular weight of FF-PAO or F-PAO is 100-20000; X is fluorine; n is an integer of 2-30; R is selected from the group consisting of: 1)A moiety of multi-branched polyethylene polymerized from ethylene, having a molecular weight of 100-20000, 2) a moiety of copolymer of ethylene and α-olefin with a chain length of 4-20 and a molecular weight of 100-20000, and 3) a moiety of polymer of isobutylene, having a molecular weight of 100-20000; wherein, FF-PAO or F-PAO is prepared by a step selected from the group consisting of: adding fluorine at terminal double bonds or other double bonds of the poly-alpha-olefins, adding fluorine at terminal double bonds or other double bonds of the polymer of monomeric alpha-olefins or mixed alpha-olefins, adding fluorine at terminal double bonds or other double bonds of the multi-branched polyethylene polymerized from ethylene, adding fluorine at terminal double bonds or other double bonds of the copolymer of ethylene and α-olefin, and adding fluorine at terminal double bonds or other double bonds of the polymer of isobutylene.

2. The halogen-containing synthetic base oil according to claim 1, wherein n is an integer of 2-10.

3. A method of preparing the halogen-containing synthetic base oil of claim 1, comprising preparing FF-PAO and/or F-PAO from PAO as follows: ##STR00009## wherein: PAO is ##STR00010## molecular weight of FF-PAO or F-PAO is 100-20000; X is fluorine; R is selected from the group consisting of: 1) A moiety of multi-branched polyethylene polymerized from ethylene, having a molecular weight of 100-20000, 2) a moiety of copolymer of ethylene and α-olefin with a chain length of 4-20 and a molecular weight of 100-20000, and 3) a moiety of polymer of isobutylene, having a molecular weight of 100-20000; wherein, preparation of FF-PAO or F-PAO is performed by a step selected from the group consisting of: adding fluorine at terminal double bonds or other double bonds of the poly-alpha-olefins, adding fluorine at terminal double bonds or other double bonds of the polymer of monomeric alpha-olefins or mixed alpha-olefins, adding fluorine at terminal double bonds or other double bonds of the multi-branched polyethylene polymerized from ethylene, adding fluorine at terminal double bonds or other double bonds of the copolymer of ethylene and α-olefin, and adding fluorine at terminal double bonds or other double bonds of the polymer of isobutylene; wherein, depending on electrophilic reaction conditions, resulting products are different as follows: 1) When fluorine is used, the resulting products are double fluorine substituted products FF-PAO, from fluorinating addition at terminal and alpha and non-terminal double bonds; 2) when hydrogen fluoride is used, the resulting products are single fluorine substituted products F-PAO, from fluorinating addition at alpha and beta positions and non-terminal double bonds.

4. A method of forming a composition of a lubricating oil from the halogen-containing synthetic base oil of claim 1, the method comprising: providing the halogen-containing synthetic base oil and additives, and mixing the halogen-containing synthetic base oil with the additives to form a composition to be used as a lubricating oil; wherein the base oil has improved water separation property and higher compatibility with additives.

5. The method according to claim 4, wherein the additives are selected from the group consisting of: (a) 0.4 wt % hindered phenol and diphenylamine antioxidants, with a feed ratio of 1:1; (b) 1.5 wt % butylated triphenyl phosphate antifriction agent; and (c) 0.1 wt % ashless rust inhibitor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flowchart illustrating a production process of synthetic mPAO.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Example 1. Synthesis of Poly-α-Decene FF-PAO6

(2) Poly-α-decene is prepared from decene-1 through a catalytic polymerization reaction. In a Teflon vessel was placed with a mixture of 200 mg of poly-α-decene and 2 mL of dichloromethane, and a solution of 200 mg of difluoroiodo-p-toluene in Et.sub.3N-THF-CH.sub.2Cl.sub.2 (1:1:2) was added dropwise at −78° C. After the addition was completed, the temperature was raised to 0° C. for 2 hours. The reaction solution was then poured into aqueous saturated sodium bicarbonate. The materials were washed three times with ether and the solvent was evaporated to dryness. The resulting materials were subjected to molecular distillation to obtain 150 mg of FF-PAO6. IR (neat): 1730 cm.sup.−1, .sup.19F NMR (376 MHz, CDCl.sub.3): δ −189.64-198.23 (m, 1F), −230.24, −230.58 (m, 1F).

Example 2. Synthesis of Poly-α-Decene F-PAO6

(3) Poly-αdecene is prepared from decene-1 through catalytic polymerization. In a Teflon vessel was placed with 200 mg of poly-α-decene and cooled to −20-30° C., and a 10 mL solution of HF in dimethyl ether was added dropwise. After the addition was completed, the reaction was warmed to room temperature for 3 hours and then quench with ice water. The materials were extracted three times with dichloromethane, and the solvent was distilled off. The resulting materials were subjected to molecular distillation to obtain 130 mg of F-PAO6. IR (neat): 1730 cm.sup.−1, .sup.19F NMR (376 MHz, CDCl.sub.3): δ −172 (m, 1F).

Example 3. Synthesis of Multi-Branched Polyethylene FF-PEO100

(4) Multi-branched polyethylene is prepared via catalytic polymerization of ethylene. In a Teflon vessel was placed with a mixed solution of 200 mg of multi-branched polyethylene and 2 mL of dichloromethane, and a solution of 200 mg of difluoroiodo-p-toluene in Et.sub.3N-THF-CH2Cl2 (1:1:2) was added dropwise at −78° C. After the dropwise addition was completed, the temperature was raised to 0° C. for 2 hours. The reaction was then poured into aqueous saturated sodium bicarbonate. The materials were washed three times with ether, and the solvent was evaporated to dryness. The resulting materials were then subjected to molecular distillation to obtain 165 mg of FF-PEO100. IR (neat): 1728 cm.sup.−1, .sup.19F NMR (376 MHz, CDCl.sub.3): δ −188.94-196.43 (m, 1F), −228.24, −228.58 (m, 1F).

Example 4. Synthesis of Multi-Branched Polyethylene F-PEO100

(5) Multi-branched polyethylene is prepared via catalytic polymerization of ethylene. In a Teflon vessel was placed with 200 mg of multi-branched polyethylene, the mixture was cooled to −20-30° C., and 10 mL solution of HF in dimethyl ether as added dropwise. After addition was completed, the temperature was raised to room temperature for 3 hours, and then the reaction was quenched with ice water. The materials were extracted three times with dichloromethane, and the solvent was distilled off. The resulting materials were molecularly distilled to obtain 132 mg of F-PEO100. IR (neat): 1728 cm.sup.−1, .sup.19F NMR (376 MHz, CDCl.sub.3): δ −170 (m, 1F).

Example 5. Base Oil Blending Test of FF-PAO6 and F-PAO6

(6) The test results of FF-PAO6 and F-PAO6 base oil blending and testing are shown in Table 1.

(7) TABLE-US-00001 TABLE 1 Base oil blending samples and test results for FF-PAO6 and F-PAO6 Alkyl compd, Compo- wt % Dispersant, sition Synthetic base oil, Alkyl wt % Blending wt % naphthalene, Dioctyl Total, sample PAO6 FF-PAO6 F-PAO6 100° C. 5 cst phthalate wt % 1 84 10 6 100 2 94 0 6 100 3 94 6 0 100 4 84 10 6 100 5 94 0 6 100 6 94 6 0 100 7 84 10 6 100 8 94 0 6 100 9 94 6 0 100 Notes: (1) PAO6 is a commercially available ordinary PAO product; (2) FF-PAO6 and F-PAO6 are PAO products with double substitution and single substitution of F, as prepared in the present invention.

(8) The base oils were blended according to the mixing ratios shown in the Table 1 above, and then mixed with the following additives, respectively, to obtain a formula-type lubricating oil composition:

(9) (1) 0.4 wt % hindered phenol and diphenylamine antioxidants, with a feed ratio of 1:1;

(10) (2) 1.5 wt % butylated triphenyl phosphate antifriction agent;

(11) (3) 0.1 wt % ashless rust inhibitor.

(12) The composition was left at 100° C. for 16 weeks, in which the blending test samples 1, 4, 5, 6, 7, 8, 9 shown no turbidity and precipitation, which indicates that the products FF-PAO6 and F-PAO6 effectively improve the solubility and dispersibility of the three types of functional additives in lubricating oil compositions.

(13) The blending test samples 2 and 3 showed trace turbidity and moderate flocculation. The appearance of turbidity and flocculation indicates insoluble phenomenon of the additives in the lubricating oil composition.

(14) Through the anti-emulsification test of ASTM-D1401 for the above blending test samples, it was found that the lubricating oil composition prepared with FF-PAO6 and F-PAO6 can be completely separated from water within 8 minutes (in the formulation of the test sample apparently there is no demulsifier). This shows that the fluorinated PAO prepared by the method of the present invention has improved water separation property.

Example 6. Base Oil Blending Test of FF-PEO100 and F-PEO100

(15) The results of blending test of FF-PEO100 and F-PEO100 base oil are shown in Table 2.

(16) TABLE-US-00002 TABLE 2 Base oil blending samples and test results for FF-PEO100 and F-PEO100 Alkyl compd, wt % Dispersant, Composition Synthetic base oil, Alkyl wt % Blending wt % naphthalene Dioctyl Total, sample PEO100 FF-PEO100 F-PEO100 100° C. 5 cst phthalate wt % 1 85 10 5 100 2 95 0 5 100 3 95 5 0 100 4 85 10 5 100 5 95 0 5 100 6 95 5 0 100 7 85 10 5 100 8 95 0 5 100 9 95 5 0 100 Notes: (1) PEO100 is a commercially available ordinary PEO product; (2) FF-PEO100 and F-PEO100 are PEO products with double substitution and single substitution of F, as synthesized in the present invention.

(17) The base oils were blended according to the mixing ratios shown in the Table 1 above, and then mixed with the following additives, respectively, to obtain a formula-type lubricating oil composition:

(18) (1) 0.4 wt % hindered phenol and diphenylamine antioxidants, with a feed ratio of 1:1;

(19) (2) 1.5 wt % butylated triphenyl phosphate antifriction agent;

(20) (3) 0.1 wt % ashless rust inhibitor.

(21) The composition was left at 100° C. for 16 weeks, in which the blending test samples 4, 5, 6, 7, 8, 9 shown no turbidity and precipitation, which indicates that the products FF-PAO100 and F-PAO100 effectively improve the solubility and dispersibility of the three types of functional additives in lubricating oil compositions.

(22) The blending test samples 1, 2 and 3 showed trace turbidity and moderate flocculation. The appearance of turbidity and flocculation indicates insoluble phenomenon of the additives in the lubricating oil composition.

(23) Through the anti-emulsification test of ASTM-D1401 for the above blending test samples, it was found that the lubricating oil composition prepared with FF-PAO100 and F-PAO100 can be completely separated from water within 8 minutes (in the formulation of the test sample apparently there is no demulsifier). This shows that the fluorinated PAO prepared by the method of the present invention has better water separation property.

(24) In summary, through the addition reaction of the double bond at the terminal or other positions of the polyalphaolefin, the introduction of polar groups improves the compatibility of the polyalphaolefin with other additives, and a series of new halogen-containing synthetic base oils groups have been obtained with enhanced property of resistance to high-temperature, water, corrosion, radiation and wear.

(25) The existing commercially available PAO-based base oils are non-polar, and when using additives, especially tackifying polymers, there have solubility problems, which have a great impact on the results of formulation. Through the addition reactions of the double bonds at the terminal or other positions of the polyalphaolefin, the introduction of polar groups improves the polarity of PAO, the solubility of additives, and thus the quality of the oils. By increasing the polarity of the lubricating oil, the firmness of the adsorbed oil film formed on the metal surface can be increased as the polarity of the molecules is increased, and the lubricating effect of the oils is enhanced as the film thickness is increased. The more polar the lubricating oil, the greater the solubility of the primary oxidation products and sludge in the oil and additives, and the lesser the sludge formation. At the same time, the increase in polar bond energy also provides activation points for bio-attack lubricant molecules, making them more easily biodegradable.

(26) Although particular embodiments and examples have been described herein in detail, the above description has been done by way of example for purposes of illustration only, and is not intended to be limiting with respect to the scope of the invention. In particular, it is contemplated by the inventor that various substitutions, alterations, and modifications may be made to the invention without departing from the scope of the invention as claimed.