CN104254515B - Mixed ester - Google Patents
Mixed ester Download PDFInfo
- Publication number
- CN104254515B CN104254515B CN201380006816.9A CN201380006816A CN104254515B CN 104254515 B CN104254515 B CN 104254515B CN 201380006816 A CN201380006816 A CN 201380006816A CN 104254515 B CN104254515 B CN 104254515B
- Authority
- CN
- China
- Prior art keywords
- acid
- mixed ester
- ester
- tetramethylolmethane
- propylheptanoic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 150000002148 esters Chemical class 0.000 title claims abstract description 195
- RXGPYPPCEXISOV-UHFFFAOYSA-N 2-propylheptanoic acid Chemical class CCCCCC(C(O)=O)CCC RXGPYPPCEXISOV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 60
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229960001735 pentaerythritol Drugs 0.000 claims abstract description 59
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethylhexanoic acid Chemical class OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 41
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N Hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 239000000314 lubricant Substances 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 91
- 238000004519 manufacturing process Methods 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- -1 aliphatic monocarboxylic acid Chemical class 0.000 description 15
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (E)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 13
- RWRIWBAIICGTTQ-UHFFFAOYSA-N Difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000003507 refrigerant Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-Tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 8
- 239000002199 base oil Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 230000000875 corresponding Effects 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FEFNFOUJRMDJFO-UHFFFAOYSA-N 2-propylheptanal Chemical compound CCCCCC(C=O)CCC FEFNFOUJRMDJFO-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 238000004821 distillation Methods 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011068 load Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N Pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NTIXPPFPXLYJCT-CFTHBVFTSA-N (3S,5R,7S,8R,9S,10S,12R,13R,14S,17R)-17-[(2R)-6-hydroxy-6-methylheptan-2-yl]-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-3,7,12-triol Chemical compound C([C@@H]1C[C@@H]2O)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCCC(C)(C)O)C)[C@@]2(C)[C@H](O)C1 NTIXPPFPXLYJCT-CFTHBVFTSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-Di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- YUAYGWBYILMNKO-UHFFFAOYSA-N 2-ethyl-3,5,5-trimethylhexanoic acid Chemical compound CCC(C(O)=O)C(C)CC(C)(C)C YUAYGWBYILMNKO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N Boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 210000001736 Capillaries Anatomy 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N Decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N Heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N Nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N Tridecylic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 230000003078 antioxidant Effects 0.000 description 2
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- 238000003556 assay method Methods 0.000 description 2
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- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- OVBFMEVBMNZIBR-RXMQYKEDSA-N (2R)-2-methylpentanoic acid Chemical compound CCC[C@@H](C)C(O)=O OVBFMEVBMNZIBR-RXMQYKEDSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-Tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 description 1
- QRMMMWOSHHVOCJ-UHFFFAOYSA-N 2,2-dimethylheptanoic acid Chemical compound CCCCCC(C)(C)C(O)=O QRMMMWOSHHVOCJ-UHFFFAOYSA-N 0.000 description 1
- ZRYCZAWRXHAAPZ-UHFFFAOYSA-N 2,2-dimethylpentanoic acid Chemical compound CCCC(C)(C)C(O)=O ZRYCZAWRXHAAPZ-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-Methyl-2-butene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- LHJPKLWGGMAUAN-UHFFFAOYSA-N 2-ethyl-2-methylbutanoic acid Chemical compound CCC(C)(CC)C(O)=O LHJPKLWGGMAUAN-UHFFFAOYSA-N 0.000 description 1
- WUWPVNVBYOKSSZ-UHFFFAOYSA-N 2-ethyl-2-methylpentanoic acid Chemical compound CCCC(C)(CC)C(O)=O WUWPVNVBYOKSSZ-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- GNKIKWFLQLKHHD-UHFFFAOYSA-N CCCCC(CC)CO[Ti] Chemical compound CCCCC(CC)CO[Ti] GNKIKWFLQLKHHD-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N Dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
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- ZUBZATZOEPUUQF-UHFFFAOYSA-N Isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N Palmitic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J Titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N Triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical class CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
The present invention provides the mixed ester of tetramethylolmethane or polyols blend and carboxylic acid, and the dipentaerythritol that described polyols blend is represented by tetramethylolmethane and formula (I) forms, and described carboxylic acid comprises 3,5,5 tri-methyl hexanoic acids and 2 propylheptanoic acids.Described mixed ester balancedly shows the performance of excellence, such as with compatibility, cryogenic property, oxidation stability, oxydrolysis stability and the lubricity of the cryogen comprising fluoropropene, have simultaneously refrigerator oil required in the range of viscosity, and can be in use in industrial lubricant such as refrigerator oil etc..
Description
Technical field
The present invention relates to a kind of mixed ester, it can be in middle uses such as Industrial Oils (such as, refrigerator oil).
Background technology
In recent years, ODP be zero hydrogen fluorohydrocarbon (HFC) be used as the cryogen for fridge etc..So
And, still there is due to HFC high global warming potential (GWP), it is therefore desirable to there is the cryogen of relatively low GWP.At present, fluorine third
Alkene cryogen such as 2,3,3,3-tetrafluoro-1-propene (hereinafter referred to " HFO-1234yf ") and 1,3,3,3-tetrafluoro-1-propene (under
Referred to herein as " HFO-1234ze ")；The mixed refrigerant etc. of fluoropropene and HFC has been considered as the candidate of this type of cryogen
(seeing patent documentation 1 and non-patent literature 1).
Fridge is generally configured such that refrigerator oil circulates at cryogen together with the cryogen of lubrication refrigerant condenser
Circulation in cycle (cycle).Therefore, refrigerator oil needs have compatibility with cryogen.Owing to refrigerator oil is used for lubricating cold
Freezing the functional unit of machine, therefore refrigerator oil also has lubricity is important.When refrigerator oil experience is separated, from freezing
The refrigerator oil that compressor is discharged may easily be trapped in the cycle.As a result, in refrigerant condenser, the amount of refrigerator oil may subtract
Few, and it may happen that insufficient lubrication, and/or expansion mechanism (such as, capillary tube) may blocking.In order to realize inside fridge
Greasy property, it is important for keeping the oil film in compressor under High Operating Temperature, and fridge oil viscosity is to maintain
The key factor of oil film.If fridge oil viscosity is low, then the thickness of oil film may reduce, and it may happen that lubricates not
Good.If fridge oil viscosity is high, then heat exchanger effectiveness may reduce (seeing patent documentation 2 and 3).
Industrial lubricant such as refrigerator oil typically requires to have and uses in low temperature environment (such as, winter or cold district)
Excellent cryogenic property, and also there is the stability of improvement.The example of stability includes heat stability, oxidation stability, oxygen
Change-hydrolytic stability etc..The equipment utilizing lubricating oil needs durability (such as, mar proof and the endurance with improvement
Property), improve energy saving capability etc..
Patent document 4 discloses that a kind of refrigerator oil, it is by tetramethylolmethane and 3, four ester compositions of 5,5-tri-methyl hexanoic acids.
But, the ester disclosed in patent documentation 4 has not satisfied cryogenic property, oxidation-hydrolytic stability etc..Patent documentation 4
Do not have open or imply described ester and the compatibility of the cryogen comprising fluoropropene.
Patent document 5 discloses that a kind of lube base oil for automobile/aero-engine/turbine etc., it comprises
2-propylheptanoic acid and four esters of tetramethylolmethane.Patent documentation 5 does not has open or implies described ester and the cryogen comprising fluoropropene
Compatibility.
Patent document 6 discloses that a kind of refrigerator oil, it comprises the ester of fatty acid mixed and tetramethylolmethane, wherein mixes fat
Fat acid is by fatty acid B and 3, and 5,5-tri-methyl hexanoic acids compositions, what described fatty acid B comprised 98.0 moles of % has 10～13 carbon
The branched chain fatty acid of atom.But, the concrete composition of the not open branched chain fatty acid with 10 carbon atoms of patent documentation 6.
Patent documentation 6 does not has open or implies described ester and the compatibility of the cryogen comprising fluoropropene.
Patent document 1 discloses that a kind of refrigerator oil, it comprises the ester of tetramethylolmethane and fatty acid mixed, described mixing fat
Fat acid is by 2 ethyl hexanoic acid and 3, and 5,5-tri-methyl hexanoic acids (mixing ratio (mol ratio): 50/50) form, and disclose described ester with
HFO-1234yf compatibility at 0 DEG C.Patent document 7 discloses that the pour point of described ester.But, lubricity of described ester etc. is no
Satisfactory, and the required performance such as industrial lubricant (such as, refrigerator oil) can not balancedly realize.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-74017 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-129177 publication
Patent documentation 3: No. 3429031 publications of Japanese Patent Publication No.
Patent documentation 4: Japanese Unexamined Patent Publication 3-200895 publication
Patent documentation 5: No. 2010/050871 pamphlet of International Publication
Patent documentation 6: No. 2008/117657 pamphlet of International Publication
Patent documentation 7: Japanese Unexamined Patent Publication 2010-90285 publication
Non-patent literature
The minutes of non-patent literature 1:2011 Japan refrigerating and air conditioning association (JSRAE) annual meeting, public good corporations
Refrigerating and air conditioning association of legal person Japan issues, page 221
Summary of the invention
Technical problem
It is an object of the invention to provide a kind of mixed ester, described mixed ester balancedly shows the performance of excellence (such as, with bag
The compatibility of the cryogen of fluorine-containing propene, cryogenic property, oxidation stability, oxidation-hydrolytic stability and lubricity), have simultaneously
Viscosity in the range of having refrigerator oil required, and can be in middle uses such as industrial lubricants (such as, refrigerator oil).
The means of solution problem
Several aspects of the invention provides herein below.
[1] mixed ester of a kind of tetramethylolmethane or polyols blend and carboxylic acid, described polyols blend by tetramethylolmethane and
The dipentaerythritol represented by lower formula (I) forms, and described carboxylic acid comprises 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid,
[2] according to mixed ester described in [1], wherein said carboxylic acid by 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid group
Become.
[3] according to the mixed ester described in [1] or [2], wherein said carboxylic acid comprises 3 with the mol ratio of 90/10～10/90,
5,5-tri-methyl hexanoic acid and 2-propylheptanoic acid.
[4] according to the mixed ester according to any one of [1]～[3], the described polyhydric alcohol wherein forming described mixed ester is
Tetramethylolmethane.
[5] a kind of refrigerator oil, it comprises according to the mixed ester according to any one of [1]～[4].
[6] a kind of working fluid composition for fridge, it comprises according to the refrigerator oil described in [5] and freezing
Agent.
Invention effect
Therefore, the present invention provides a kind of mixed ester, described mixed ester balancedly show excellence performance (such as, with comprise
The compatibility of the cryogen of fluoropropene, cryogenic property, oxidation stability, oxidation-hydrolytic stability and lubricity), have simultaneously
Viscosity in the range of refrigerator oil is required, and can be in middle uses such as industrial lubricants (such as, refrigerator oil).
Detailed description of the invention
What the mixed ester of the present invention was tetramethylolmethane with the carboxylic acid comprising 3,5,5 Trimethylhexanoic acid and 2-propylheptanoic acid is mixed
Close ester；Or the mixed ester of polyols blend and carboxylic acid, wherein said polyols blend by tetramethylolmethane and is represented by lower formula (I)
Dipentaerythritol forms, and wherein said carboxylic acid comprises 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid.
Terms used herein " mixed ester " refers to by using the multiple carboxylic acid forming ester together with polyhydric alcohol to carry out ester
The compound changed and obtain.
Hereinafter, the tetramethylolmethane of the mixed ester of the present invention is formed or by mixing that tetramethylolmethane and dipentaerythritol form
Close polyhydric alcohol and be referred to as " composition alcohol ", and the carboxylic acid forming the mixed ester of the present invention is referred to as " composition carboxylic acid ".
The mixed ester of the present invention includes: (i) constitutes carboxylic acid and constitute the mixed ester of alcohol, wherein, constitutes carboxylic acid at one point
Son comprises both 3,5,5 Trimethylhexanoic acid and 2-propylheptanoic acid；(ii) alcohol and the structure comprising 3,5,5 Trimethylhexanoic acid are constituted
Become the ester of carboxylic acid and constitute alcohol and the mixture of the ester constituting carboxylic acid comprising 2-propylheptanoic acid；(iii) (i) and (ii's) is mixed
Compound.
The mixed ester of the present invention can comprise some hydroxyls wherein constituting alcohol as impurity the most esterified part ester.
Constitute carboxylic acid and can comprise other carboxylic acid in addition to 3,5,5 Trimethylhexanoic acid and 2-propylheptanoic acid.Other carboxylic acid
Example includes linear aliphatic monocarboxylic acid (such as, acetic acid, propanoic acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, dodecylic acid, the tetradecane
Acid, hexadecanoic acid and octadecanoid acid), branched aliphatic monocarboxylic acid (such as, 2 Ethylbutanoic acid, 2 methyl valeric acid, 4-methylpent
Acid, 2 methyl caproic acid, 2-ethylpentanoic, 2-Ethyl-2-Methyl butanoic acid, 2,2-dimethyl valeric acid, 2-methyl enanthic acid, 3-ethyl hexyl
Acid, 2-Ethyl-2-Methyl valeric acid, 2-methyloctanoic acid, 2,2-dimethyl enanthic acid, different tridecanoic acid and isostearic acid) etc..
Constituting the content of other carboxylic acid in carboxylic acid can be in the range of following: do not damage the excellent properties of mixed ester of the present invention
(such as, with compatibility, cryogenic property, oxidation stability, oxidation-hydrolytic stability and the lubrication of the cryogen comprising fluoropropene
Property), have simultaneously refrigerator oil required in the range of viscosity.
Constitute the total content of 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid in carboxylic acid and be preferably 50 moles of more than %, more excellent
Elect 80 moles of more than %, still more preferably 90 moles more than % as.Most preferably, constitute carboxylic acid by 3,5,5-tri-methyl hexanoic acids and
2-propylheptanoic acid forms.
Viscosity in the range of needed for refrigerator oil and comprise the compatibility of cryogen of fluoropropene, cryogenic property, oxidation
From the point of view of the viewpoints such as stability, oxidation-hydrolytic stability, 3,5,5-tri-methyl hexanoic acids to the mol ratio of 2-propylheptanoic acid (that is, 3,5,
5-tri-methyl hexanoic acid/2-propylheptanoic acid) be preferably 90/10～10/90, more preferably 90/10～15/85, even more preferably from 80/20～
30/70.Constitute the content of 2-propylheptanoic acid in carboxylic acid and be preferably 10 moles of more than %.
When constituting the polyols blend that alcohol is made up of tetramethylolmethane and dipentaerythritol, scope needed for refrigerator oil
In the compatibility of viscosity and the cryogen comprising fluoropropene, from the point of view of the viewpoint such as cryogenic property, constitute dipentaerythritol in alcohol
Content is preferably 30 moles of below %, more preferably 20 moles below %.It is more preferred still that gluing in the range of needed for refrigerator oil
From the point of view of spending the viewpoints such as the compatibility with the cryogen comprising fluoropropene, cryogenic property, constitute alcohol and only comprise tetramethylolmethane.
About the polyols blend forming mixed ester of the present invention being made up of tetramethylolmethane and dipentaerythritol, it is possible to use
Commercially available prod, or it can be by prepare commercially available tetramethylolmethane and the mixing of commercially available dipentaerythritol.
The 2-propylheptanoic acid forming mixed ester of the present invention can (such as, Japanese Unexamined Patent Publication 8-109299 in accordance with known methods
Method disclosed in number publication) manufacture: by valeral being carried out aldol condensation to obtain unsaturation in the presence of base catalyst
Aldehyde, hydrogenates the double bond of described unsaturated aldehyde, and aoxidizes products therefrom.The 2-propylheptanoic acid forming mixed ester of the present invention can also lead to
Cross and such as make amylene two coalescence oxidation products therefrom manufacture (seeing DE10239134).
The mixed ester of the present invention can be by such as making composition alcohol, 3,5,5 Trimethylhexanoic acid, 2-propylheptanoic acid and optionally
Other carboxylic acid react 5～60 hours at 120 DEG C～300 DEG C and manufacture.In this case, all carboxylic acids can add simultaneously
Enter, or every kind of carboxylic acid can be sequentially added into.For example, it is possible to mix all carboxylic acids, and it is made to react (manufacture method with constituting alcohol
1)；Or this can make composition alcohol, 2-propylheptanoic acid and other optional carboxylic acid with specific quantitative response, and can successively to
Mixture adds 3,5,5 Trimethylhexanoic acid to react (manufacture method 2) with them.
Owing to 2-propylheptanoic acid has low reaction speed with constituting alcohol, therefore, manufacture and constitute alcohol and comprise 2-propylheptanoic acid
The mixed ester of carboxylic acid may compare the cost time.However, it is possible to by according to constituting 3,5,5-tri-methyl hexanoic acids pair in carboxylic acid
The ratio of 2-propylheptanoic acid properly selects manufacture method 1 or 2 and shortens the time manufactured needed for mixed ester of the present invention.Specifically
Ground, is tetramethylolmethane when constituting alcohol, and 3, (3,5,5-trimethyls are own to the mol ratio of 2-propylheptanoic acid for 5,5-tri-methyl hexanoic acids
Acid/2-propylheptanoic acid) when being 30/70～95/5, the mixed ester of the present invention can utilize manufacture method 1 or 2 when comparatively short
Interior manufacture.It is tetramethylolmethane when constituting alcohol, and 3,5, the 5-tri-methyl hexanoic acids mol ratio (3,5,5-tri-to 2-propylheptanoic acid
Methylhexanoic acid/2-propylheptanoic acid) when being 5/95～30/70 (not including 30/70), the mixed ester of the present invention can be by selection system
Make method 2 (such as, less than 25 hours) within the comparatively short time to manufacture.Therefore, the mixed ester of the present invention can be with high production rate
Manufacture.
When the mixed ester using manufacture method 1 or 2 to manufacture the present invention, the performance of the mixed ester of the present invention is (such as, with bag
The compatibility of the cryogen of fluorine-containing propene, cryogenic property, oxidation stability, oxidation-hydrolytic stability and lubricity) intact.
Catalyst can be used during manufacturing the reaction of mixed ester of the present invention.The example of catalyst include mineral acid,
Organic acid, lewis acid, metallo-organic compound, solid acid etc..The instantiation of mineral acid include hydrochloric acid, Fluohydric acid., sulphuric acid,
Phosphoric acid, nitric acid etc..The instantiation of organic acid includes p-methyl benzenesulfonic acid, benzenesulfonic acid, fourth sulfonic acid, propane sulfonic acid, ethyl sulfonic acid, methanesulfonic acid
Deng.Lewis acidic instantiation includes boron trifluoride, aluminum chloride, butter of tin, titanium tetrachloride etc..Metal-organic
Instantiation includes four titanium propanolates, four titanium butoxide, four (2-ethyl hexyl oxy) titanium etc..The instantiation of solid acid includes sun
Ion exchange resin etc..
Preferably react while removing the water during reaction generated from reactant mixture.
The amount (mole) of the amount (mole) of 3,5,5 Trimethylhexanoic acid, the amount (mole) of 2-propylheptanoic acid and other carboxylic acid
With the amount (mole) being preferably the hydroxyl constituting alcohol 1.1～1.4 times.
During reaction can use solvent.The example of solvent includes solvent based on hydrocarbon (such as, benzene, toluene, diformazan
Benzene, hexane, heptane, isohexane, isobutyltrimethylmethane., isononane and decane) etc..
Due to 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid mix for the difference between the reactivity of composition alcohol, gained
In ester, 3,5,5 Trimethylhexanoic acid is to the mol ratio of 2-propylheptanoic acid and the 3,5,5 Trimethylhexanoic acid pair for manufacturing mixed ester
The mol ratio of 2-propylheptanoic acid may be different.
After completion of the reaction, optionally use be generally used in synthetic organic chemistry method (such as, with water and/or
Alkaline aqueous solution washs；Process with activated carbon, adsorbent etc.；Chromatography；Or distillation) gained mixed ester is purified.
Owing to the mixed ester of the present invention comprises 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid are as constituting carboxylic acid, therefore,
Mixed ester balancedly shows the performance of excellence (such as, with the compatibility of the cryogen comprising fluoropropene, viscosity versus temperature performance, low
Warm nature energy, stability and lubricity) and enough performance (such as, low temperature flow and electrical insulation capability), there is freezing simultaneously
Viscosity in the range of machine oil is required.The mixed ester of the present invention refrigerator oil to the present invention and the working fluid group for fridge
Compound provides excellent lubricity.
When using the mixed ester of the present invention in refrigerator oil, refrigerator oil has enough lubricity (such as, frictions
Reduction ability and abrasion reduction ability (abrasion resistance properties)) it is important.The lubricity of refrigerator oil is generally by refrigerator oil
Viscosity influence.If fridge oil viscosity is the lowest, then the thickness of the oil film of sliding position may reduce, and wear extent may increase
Add.As a result, the life-span using the equipment etc. of lubricating oil is tended to shorten.If fridge oil viscosity is the highest, then viscous drag
May increase, and coefficient of friction may increase.As a result, energy efficiency is tended to reduce.Therefore, mixed ester needs have fridge
Viscosity in the range of oil is required.
When using the mixed ester of the present invention in refrigerator oil, it is important that mixed ester and cryogen have compatibility.
If mixed ester is not enough with the compatibility of cryogen, then cryogen and refrigerator oil may experience be separated, and from freezing pressure
The refrigerator oil that contracting machine is discharged may be trapped in cryogen cycle period, lubrication thus may occur in refrigerant condenser not
Good.When making in needing the refrigerator oil of abrasion resistance properties of long period (such as, for the refrigerator oil of air conditioner)
During with the mixed ester of the present invention, if mixed ester is the highest with the compatibility of cryogen, then cryogen in cryogen cycle period
May reduce with the viscosity (viscosity of cryogen solution) of the mixture of refrigerator oil, and the thickness of the oil film of sliding position can
Can reduce, thus it may happen that insufficient lubrication.The reduction of the viscosity of cryogen solution is likely to cause the cunning of refrigerant condenser
The sealing property of the cryogen in dynamic position reduces.Therefore, mixed ester need to have refrigerator oil required in the range of compatibility.
Two-phase laminated flow temperature is generally used to be evaluated with the compatibility of cryogen.Think when two-phase laminated flow temperature is low,
It is good with the compatibility of cryogen at low temperature side.When using the mixed ester of the present invention in refrigerator oil, mixed ester needs
Two-phase laminated flow temperature (representing compatibility degree) in the range of refrigerator oil to be had is required.The present invention is used in refrigerator oil
Mixed ester in the case of, the two-phase laminated flow temperature of mixture of mixed ester (10%) and the cryogen that comprises fluoropropene is the most excellent
Elect less than-10 DEG C as, more preferably-10 DEG C～-50 DEG C.Relevant with the performance of mixed ester with the compatibility of cryogen.
Viscosity versus temperature performance refers to the kinematic viscosity change relative to the variations in temperature of oil solution (such as, lubricating oil).Table
The oil solution of existing excellent viscosity versus temperature performance shows little viscosity B coefficent relative to variations in temperature.The viscosity versus temperature of performance difference
At low-temperature region, the oil solution of performance shows that quick viscosity increases, or the notable fall at high-temperature area display kinematic viscosity
Low.Viscosity versus temperature performance is generally represented by viscosity index (VI).Think that, when viscosity index (VI) height, viscosity versus temperature performance is good.
Viscosity performance at low-temperature region is referred to as low temperature flow, and is represented by pour point, freezing point, channel point etc..
Terms used herein " pour point " refers to, the method for regulation makes according to Japanese Industrial Standards (JIS) K 2269
During oil solution cooling, the minimum temperature that oil solution (such as, lubricating oil) flows.The equipment just utilizing oil solution will not operate
For bad, even if the oil solution with low pour point is preferably as described oil solution is in experience low temperature environment (such as, the winter
Season or cold district) time also will not show the deterioration of mobility.
When the local long-time storage changed to a great extent in temperature or use oil solution (such as, lubricating oil)
Time, it is preferred that oil solution does not show volatility etc. at high-temperature area, and does not show solidification, precipitation etc. at low-temperature region.Temperature
Degree scope is not particularly limited.Preferably, oil solution stably can make within the temperature range of about-20 DEG C～about 150 DEG C
With.Terms used herein " cryogenic property " refers at low-temperature region, solidification to occur and separate out.
The term " stability " being used in combination with lubricating oil application includes heat stability, oxidation stability, oxidation-hydrolysis surely
Qualitative, shear stability etc..
Terms used herein " electrical insulation capability " is represented by specific insulation, and according to the side of regulation in JIS C2101
Method is measured.When at oil solution (such as, lubricating oil) middle use motor etc., oil solution needs have good electric insulation
Performance.
Terms used herein " lubricity " refers to rub reduction ability, abrasion reduction ability (abrasion resistance properties), extreme pressure
Performance etc..In cryogen cycle period, cryogen is generally present in sliding position together with refrigerator oil.Therefore, when
Refrigerator oil or when using the mixed ester of the present invention in the working fluid composition of fridge, mixed ester needs at cryogen
There is in the presence of (such as, comprising the cryogen of fluoropropene) lubricity of excellence.
When using the mixed ester of the present invention in refrigerator oil, it is preferred that mixed ester kinematic viscosity at 40 DEG C
For 20mm2/ s～150mm2/ s, more preferably 30mm2/ s～110mm2/ s, still more preferably 60mm2/ s～110mm2/s。
In the case of using the mixed ester of the present invention in refrigerator oil, if great amount of hydroxy group remains in mixed ester, then
It may happen that the less desirable phenomenon of refrigerator oil (such as, the blocking of capillary device in muddiness, freeze cycle under low temperature).Cause
This, it is preferred that mixed ester has the hydroxyl value of below 10mg KOH/g, more preferably below 5mg KOH/g.
The refrigerator oil of the present invention comprises the mixed ester of the present invention.Such as, described refrigerator oil can be only by described mixing
Ester forms, or can be made up of described mixed ester and other lube base oil.Described refrigerator oil can optionally enter one
Step comprises additive for lubricant.Refrigerator oil comprises mixed ester as lube base oil.
The example of additive for lubricant includes that detergent dispersant additive, antioxidant, abrasion depressant are (such as, resistance to
Abrasion agent, anti-bite mixture and extreme pressure agent), friction improver, oiliness improver, plumper, matal deactivator, antirust agent, pour point decline
Agent, viscosity index improver, thickening agent, defoamer etc..Each additive content in refrigerator oil is preferably 0.001 weight %
～5 weight %.
The example of antioxidant includes ditertbutylparacresol etc..Abrasion depressant example include tricresyl phosphate,
Triphenyl phosphate etc..The example of plumper include 2-ethylhexyl glycidyl ether, new decyl glycidyl esters, double (two
Butyl phenyl) carbodiimides etc..The example of matal deactivator includes benzotriazole etc..The example of defoamer includes dimethyl-silicon
Oxygen alkane etc..
The example of other lube base oil includes mineral oil, synthetic base oil etc..
The example of mineral oil includes paraffinic base crude oil, intermediate base crude, naphthene base crude etc..Can also use by via
Any described mineral oil of the purification such as distillation and the refined oil that obtains.
The example of synthetic base oil includes poly alpha olefin (such as, polybutene, polypropylene and have 8～14 carbon atoms
Alpha-olefin low polymers), aliphatic (acid) ester (such as, fatty-acid monoester, the fatty acid ester of polyhydric alcohol and fat in addition to mixed ester of the present invention
Race's polybasic ester), aromatic ester (such as, aromatics monoesters, the aromatic ester of polyhydric alcohol and aromatic polybasic acid esters), polyalkylene two
Alcohol, polyvinylether, Merlon, alkylbenzene etc..
In refrigerator oil, the content of other lube base oil is not particularly limited, if various performance (such as, with comprise
The compatibility of the cryogen of fluoropropene, low temperature flow and lubricity) it is without prejudice, in the range of having needed for refrigerator oil simultaneously
Viscosity.In refrigerator oil, the content of other lube base oil is preferably below 70 weight %, more preferably 50 weight %
Hereinafter, below 40 weight %, below most preferably 30 weight %.
The working fluid composition for fridge of the present invention comprises the refrigerator oil of cryogen and the present invention.The present invention
Mixed ester in the refrigerator oil that is included in the working fluid composition of fridge.The refrigerator oil of the present invention and
Cryogen can mix with arbitrary proportion.Be preferably based on 100 weight portion cryogens with 1～1000 weight portions, more preferably 2～800
The amount of weight portion uses the mixed ester of the present invention.
From the viewpoint of guaranteeing low GWP and compatibility within the required range, it is included in the workflow for fridge
Cryogen in body compositions preferably comprises selected from fluoropropene, the hydrocarbon and at least the one of carbon dioxide with 3～5 carbon atoms
Plant the cryogen of compound.Wherein, the cryogen comprising fluoropropene is preferred.Comprise the example bag of the cryogen of fluoropropene
Include only be made up of fluoropropene cryogen, by fluoropropene and hydrogen fluorohydrocarbon (such as, difluoromethane (hereinafter referred to " HFC-32 "))
The mixed refrigerant etc. of composition.The example of the cryogen being only made up of fluoropropene include HFO-1234ze, HFO-1234yf, they
Mixture etc..Wherein, HFO-1234ze or HFO-1234yf is preferred.
The example of the mixed refrigerant being made up of fluoropropene and hydrogen fluorohydrocarbon (such as, HFC-32) includes HFO-1234ze/
HFC-32 (that is, the mixed refrigerant being made up of HFO-1234ze and HFC-32), HFO-1234yf/HFC-32 are (that is, by HFO-
The mixed refrigerant of 1234yf and HFC-32 composition) etc..Wherein, HFO-1234ze/HFC-32 is preferred.Fluoropropene and hydrogen fluorine
The mixing ratio of hydrocarbon is not particularly limited.
Except refrigerator oil and for fridge working fluid composition in addition to, the mixed ester of the present invention also can start
Machine oil, gear oil, the electric motor oil for motor vehicle driven by mixed power or electric vehicle, grease, metal parts cleaning agent, plasticizer
Use in Deng.The refrigerator oil of the present invention and the working fluid composition for fridge can be preferred for room air regulation
Device, unitary air conditionary, air conditioner in car, dehumidifier, freezer, freezer, freezing-cooling storeroom, automatic vending
Machine, showcase, the fridge etc. that is arranged in such as chemical plant.
Embodiment
The present invention is further described hereinafter by manufacturing example, embodiment, comparative example and test example.But, the present invention is also
It is not limited to following example.
Following determining instrument and assay method is used to measure NMR (Nuclear Magnetic Resonance) spectrum.
Determining instrument: GSX-400 (400mHz), by NEC, company manufactures
Assay method:1H-NMR (standard substance: tetramethylsilane, solvent: CDCl3)
Measure the NMR (Nuclear Magnetic Resonance) spectrum of the mixed ester manufactured in embodiment 1～8, and calculated in mixed ester by following expression formula
The 3,5,5 Trimethylhexanoic acid mol ratio to 2-propylheptanoic acid.
The integrated value of 3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid=peak A/(integrated value of the integrated value of peak B-peak A)
In above-mentioned expression formula, peak A is corresponding to the hydrogen atom on the methylene of the α position of the carbonyl of 3,5,5-tri-methyl hexanoic acids
Peak in the peak of a hydrogen atom of side, highfield；And peak B is corresponding to the methylene of the α position of the carbonyl of 3,5,5 Trimethylhexanoic acid
In the peak of the hydrogen atom on base on the methine of the α position of the carbonyl of the peak of a hydrogen atom of downfield side and 2-propylheptanoic acid
The sum at the peak of one hydrogen atom.
By following expression formula calculate tetramethylolmethane in the mixed ester manufactured in embodiment 7 and 8 to dipentaerythritol mole
Ratio.
Tetramethylolmethane/dipentaerythritol=(integrated value/8 of peak C)/(integrated value/4 of peak D)
In above-mentioned expression formula, peak C is corresponding to the peak of 8 hydrogen atoms on the methylene of tetramethylolmethane；And peak D is corresponding
The peak of 4 hydrogen atoms on the methylene being bonded to ether oxygen atom of dipentaerythritol.
Measure the NMR (Nuclear Magnetic Resonance) spectrum of the mixed ester manufactured in comparative example 3, and calculated 2-in mixed ester by following expression formula
The thylhexoic acid mol ratio to 3,5,5 Trimethylhexanoic acid.
2 ethyl hexanoic acid/3,5,5 Trimethylhexanoic acid=(integrated value of the integrated value of peak E-peak A)/(integrated value of peak A)
In above-mentioned expression formula, peak A is as defined above；And peak E is corresponding to the carbonyl of 3,5,5 Trimethylhexanoic acid
α position methylene on hydrogen atom peak in the α position of carbonyl of peak and 2 ethyl hexanoic acid of a hydrogen atom of downfield side
Methine on the sum at peak of a hydrogen atom.
[manufacture example]
[manufacturing 2-propylheptanoic acid]
(1) 2-propyl group-2-heptenic aldehyde is manufactured
20g (0.5 mole) sodium hydroxide is loaded (by Northeast chemistry in the reactor being equipped with Dropping funnel and condenser
Company manufactures) and 500mL water.While stirring mixture at 80 DEG C, with 3.5 hours by 2434g (28.3 moles) valeraldehyde
(" valeral " that manufactured by Tokyo chemical conversion industrial group) is added drop-wise to mixture from Dropping funnel.Mixture is stirred at 95 DEG C
2 hours, then remove water layer from product.By distillation (boiling point: 70 DEG C/0.7 kPa) purification reaction product, obtain
1930g 2-propyl group-2-heptenic aldehyde.
(2) 2-propyl heptanal is manufactured
In autoclave, (water content: 56%, by grace hundred million for loading 420g 2-propyl group-2-heptenic aldehyde and 4g 5%Pd carbon dust
Kai Jia company (N.E.Chemcat Corporation) manufacture), and by mixture at 75 DEG C under the Hydrogen Vapor Pressure of 1.5mPa
Stir 1.5 hours.Product is filtered by film filter (PTFE, 0.5 μm), it is thus achieved that 416g 2-propyl heptanal.
(3) 2-propylheptanoic acid is manufactured
0.2g (0.005 mole) sodium hydroxide (chemical company manufactures by the Northeast), 1g water and 0.8g is loaded in reactor
(0.006 mole) enanthic acid (is manufactured by キ シ ダ chemical company), and stirs mixture.After adding 47g 2-propyl heptanal, will
Mixture uses air bubbling 15 hours at 40 DEG C.Mixture is stirred 4 hours under nitrogen bubble at 130 DEG C, it is thus achieved that thick
The 2-propylheptanoic acid of system.
In another reactor load 4g (0.1 mole) sodium hydroxide (chemical company manufactures by the Northeast), 36g water and
2-propylheptanoic acid rough for 17g, and stir mixture.After adding 734g 2-propyl heptanal, mixture is used at 40 DEG C sky
Gas bell 14 hours.Mixture is stirred 5 hours under nitrogen bubble at 120 DEG C, it is thus achieved that 2-propylheptanoic acid rough for 804g.
By distillation (boiling point: 156 DEG C～157 DEG C/0.4 kPa) rough for purification 774g 2-propylheptanoic acid, it is thus achieved that 520g2-propyl group heptan
Acid.
1H-NMR(CDCl3,δppm)；0.88(t,3H),0.92(t,3H),1.29-1.50(m,10H),1.58-1.67(m,
2H),2.33-2.40(m,1H)
[embodiment 1]
[manufacture tetramethylolmethane and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein mol ratio (3,5,5-
Tri-methyl hexanoic acid/2-propylheptanoic acid) be 90/10 (mixed ester 1)]
Commercially available prod " Kyowaad 500 " (by consonance, chemical industrial company manufactures) is used as adsorbent.
Commercially available prod " egression P " (by Japanese Environment, chemical company manufactures) is used as activated carbon.
110g (0.8 mole) tetramethylolmethane is loaded (by wide Rong Bai in the reactor being equipped with Dean-Stark water knockout drum
Si Tuo company manufactures), (0.4 rubs for 553g (3.5 moles) 3,5,5 Trimethylhexanoic acid (being manufactured by KH Xin Hua Co., Ltd.) and 67g
You) 2-propylheptanoic acid (see above-mentioned manufacture example).By at room temperature, under the decompression of 20 kPa, under agitation nitrogen bubble 30
Minute and mixture is de-gassed.
By mixture at 184 DEG C～233 DEG C at atmosheric pressure at nitrogen bubble under stir 12 hours.Complete in reaction
After, product is stirred 2 hours at 164 DEG C～235 DEG C under the decompression of 0.9 kPa, thus removes from product
Unreacted carboxylic acid.With 200mL, product is contained sodium hydroxide at 90 DEG C, and (relative to the acid number of product, 2 times are rubbed
Your number) alkaline aqueous solution wash 0.5 hour.Then, product is washed 0.5 hour (three with 200mL water at 90 DEG C
Secondary).Then, product is stirred at 90 DEG C under the decompression of 0.9 kPa under nitrogen bubble 1 hour with dry reaction product
Thing.
Adding 4.0g adsorbent (corresponding to the product of 0.7 weight %) and 2.9g activated carbon (corresponding to 0.5 weight
The product of amount %) after, mixture is stirred 2 hours at 100 DEG C under the decompression of 1.3 kPa under nitrogen bubble.So
After, use filtration adjuvant filtering mixt, it is thus achieved that 516g mixed ester 1.
[embodiment 2]
[manufacture tetramethylolmethane and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein mol ratio (3,5,5-
Tri-methyl hexanoic acid/2-propylheptanoic acid) be 77/23 (mixed ester 2)]
Mixed ester 2 obtains in the same manner as example 1, and difference is, by tetramethylolmethane, 3,5,5-trimethyls
The mol ratio (tetramethylolmethane/3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid) of caproic acid and 2-propylheptanoic acid changes into 1/3.36/
1.44, and will change in the response time 14 hours.
[embodiment 3]
[manufacture tetramethylolmethane and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein mol ratio (3,5,5-
Tri-methyl hexanoic acid/2-propylheptanoic acid) be 50/50 (mixed ester 3)]
Mixed ester 3 obtains in the same manner as example 1, and difference is, by tetramethylolmethane, 3,5,5-trimethyls
The mol ratio (tetramethylolmethane/3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid) of caproic acid and 2-propylheptanoic acid changes into 1/2.20/
2.60, and will change in the response time 15 hours.
[embodiment 4]
[manufacture tetramethylolmethane and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein mol ratio (3,5,5-
Tri-methyl hexanoic acid/2-propylheptanoic acid) be 34/66 (mixed ester 4)]
Mixed ester 4 obtains in the same manner as example 1, and difference is, by tetramethylolmethane, 3,5,5-trimethyls
The mol ratio (tetramethylolmethane/3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid) of caproic acid and 2-propylheptanoic acid changes into 1/1.45/
3.35, and will change in the response time 17 hours.
[embodiment 5]
[manufacture tetramethylolmethane and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein mol ratio (3,5,5-
Tri-methyl hexanoic acid/2-propylheptanoic acid) be 19/81 (mixed ester 5)]
Mixed ester 5 obtains in the same manner as example 1, and difference is, by tetramethylolmethane, 3,5,5-trimethyls
The mol ratio (tetramethylolmethane/3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid) of caproic acid and 2-propylheptanoic acid changes into 1/0.80/
4.00, and will change in the response time 30 hours.
[embodiment 6]
[manufacture tetramethylolmethane and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein mol ratio (3,5,5-
Tri-methyl hexanoic acid/2-propylheptanoic acid) be 16/84 (mixed ester 6)]
68g (0.5 mole) tetramethylolmethane is loaded in the reactor being equipped with Dean-Stark water knockout drum and Dropping funnel
(being manufactured by Guang Rong Bai Situo company) and 331g (1.9 moles) 2-propylheptanoic acid (see above-mentioned manufacture example).By at room temperature,
Under the decompression of 20 kPa, under agitation mixture is de-gassed by nitrogen bubble for 30 minutes.
By mixture at 180 DEG C～230 DEG C at atmosheric pressure at nitrogen bubble under stir 7 hours.Leaking from dropping liquid
After bucket adds 76g (0.5 mole) 3,5,5-tri-methyl hexanoic acid (being manufactured by KH Xin Hua Co., Ltd.), by mixture at 230 DEG C
Stir 11 hours.Total reaction time is 18 hours.
After completion of the reaction, carry out follow-up operation in the same manner as example 1 (to remove unreacted carboxylic acid, use
Alkaline aqueous solution washs, and washes with water, is dried, with adsorbent and activated carbon adsorption and filtration), it is thus achieved that 291g mixed ester 6.
[embodiment 7]
[manufacture tetramethylolmethane and dipentaerythritol and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein
Mol ratio (tetramethylolmethane/dipentaerythritol) is 90/10 and mol ratio (3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid) is 56/
44 (mixed esters 7)]
Mixed ester 7 obtains in the same manner as example 1, and difference is, use by mixing tetramethylolmethane (by
Guang Rong Bai Situo company manufactures) and dipentaerythritol (being manufactured by Guang Rong Bai Situo company) and the mixed alcohol replacement Ji Wusi for preparing
Alcohol, by mol ratio (tetramethylolmethane/bis-season penta of tetramethylolmethane, dipentaerythritol, 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid
Tetrol/3,5,5-tri-methyl hexanoic acids/2-propylheptanoic acid) change into 1/0.11/2.80/2.80, and the response time will change into 27
Hour.
[embodiment 8]
[manufacture tetramethylolmethane and dipentaerythritol and 3,5,5-tri-methyl hexanoic acids and the mixed ester of 2-propylheptanoic acid, wherein
Mol ratio (tetramethylolmethane/dipentaerythritol) is 80/20 and mol ratio (3,5,5 Trimethylhexanoic acid/2-propylheptanoic acid) is 30/
70 (mixed esters 8)]
Mixed ester 8 obtains in the same manner as example 1, and difference is, use by mixing tetramethylolmethane (by
Guang Rong Bai Situo company manufactures) and dipentaerythritol (being manufactured by Guang Rong Bai Situo company) and the mixed alcohol replacement Ji Wusi for preparing
Alcohol, by mol ratio (tetramethylolmethane/bis-season penta of tetramethylolmethane, dipentaerythritol, 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid
Tetrol/3,5,5-tri-methyl hexanoic acids/2-propylheptanoic acid) change into 1/0.25/1.85/4.75, and the response time will change into 43
Hour.
[comparative example 1]
[manufacturing the ester (ester A) of 3,5,5 Trimethylhexanoic acid and tetramethylolmethane]
Ester A obtains in the same manner as example 1, and difference is, only uses 3,5,5-tri-methyl hexanoic acid conducts
Carboxylic acid, by tetramethylolmethane to 3, the mol ratio (tetramethylolmethane/3,5,5-tri-methyl hexanoic acids) of 5,5-tri-methyl hexanoic acids changes into 1/
4.80, and will change in the response time 9 hours.
[comparative example 2]
[manufacturing the ester (ester B) of 2-propylheptanoic acid and tetramethylolmethane]
Ester B obtains in the same manner as example 1, and difference is, only use 2-propylheptanoic acid, will as carboxylic acid
The mol ratio (tetramethylolmethane/2-propylheptanoic acid) of 2-propylheptanoic acid is changed into 1/4.80 by tetramethylolmethane, and will change in the response time
Become 31 hours.
[comparative example 3]
[manufacture tetramethylolmethane and 2 ethyl hexanoic acid and 3, the mixed ester of 5,5-tri-methyl hexanoic acids, wherein mol ratio (2-ethyl
Caproic acid/3,5,5 Trimethylhexanoic acid) be 50/50 (mixed ester C)]
Mixed ester C obtains in the same manner as example 1, and difference is, (is newly changed strain by KH with 2 ethyl hexanoic acid
Formula commercial firm manufactures) replace 2-propylheptanoic acid, by tetramethylolmethane, 2 ethyl hexanoic acid and 3, the mol ratio (season of 5,5-tri-methyl hexanoic acids
Penta tetrol/2 ethyl hexanoic acid/3,5,5-tri-methyl hexanoic acids) change into 1/2.69/2.11, and it is little the response time will to change into 32
Time.
The mensuration of (test example 1) kinematic viscosity
Cannon-Fenske viscometer is used to measure mixed ester and ester according to the method for regulation in JIS K 2283:2000
(mixed ester 1～8, ester A, ester B and mixed ester C) kinematic viscosity at 40 DEG C and 100 DEG C.According in JIS K 2283:2000
The method of regulation calculates viscosity index (VI).Result is shown below and in Tables 1 and 2.
The mensuration (evaluation of compatibility) of (test example 2) two-phase laminated flow temperature
Mixed ester and ester (mixed ester 1～8, ester A and ester B) is measured according to the method for regulation in JIS K 2211:2009
Two-phase laminated flow temperature.
[with the evaluation of the compatibility of HFO-1234yf]
0.4g mixed ester or ester (mixed ester 1～8, ester A or ester B) and 3.6g HFO-is loaded in pressure glass tubing
1234yf (is manufactured by Honeywell Int Inc), and by mixture with the speed of 0.5 DEG C/min from 30 DEG C of coolings.Will mixing
Thing is divided into temperature that is biphase or that become muddiness and is defined as two-phase laminated flow temperature.Result is shown in Tables 1 and 2.
[with the evaluation of the compatibility of HFO-1234ze/HFC-32 (weight ratio: 60/40)]
1) mixed refrigerant is manufactured
Weight ratio (HFO-1234ze/HFC-32) with 60/40, loads HFO-1234ze (by Buddhist nun suddenly in pressure vessel
Wei Er international corporation manufacture) and HFC-32 (company manufactures by Daikin Industries) to manufacture mixed refrigerant.Receive from pressure vessel
The liquid phase of collection mixed refrigerant, and use it for the mensuration of following two-phase laminated flow temperature.
2) mensuration of two-phase laminated flow temperature
0.4g mixed ester or ester (mixed ester 1～8, ester A or ester B) and 3.6g mixed freezing is loaded in pressure glass tubing
Agent, and by mixture with the speed of 0.5 DEG C/min from 30 DEG C of coolings.Mixture is divided into temperature that is biphase or that become muddiness determine
For two-phase laminated flow temperature.Result is shown in Tables 1 and 2.
[with the evaluation of the compatibility of HFO-1234ze]
0.4g mixed ester (mixed ester 2,4 or 8) and 3.6gHFO-1234ze is loaded (by Honeywell in pressure glass tubing
International corporation manufactures), and by mixture with the speed of 0.5 DEG C/min from 30 DEG C of coolings.Mixture it is divided into biphase or becomes muddiness
Temperature be defined as two-phase laminated flow temperature.Result is illustrated below.
(test example 3) measures whether there is solidification/precipitate (evaluation of cryogenic property) at-20 DEG C
1.0g mixed ester or ester (mixed ester 1～8, ester A or ester B) are put in glass container, and makes it be set in-20
DEG C calorstat in stand 24 hours.Little constantly when the past 24, determine whether there is solidification/precipitate by visualization.Will
Do not observe that the situation of solidification/precipitate is evaluated as " qualified ", and it will be observed that the situation of solidification/precipitate is evaluated as " not conforming to
Lattice ".Result is shown in Tables 1 and 2.
The mensuration (oxidation-hydrolytic stability and the evaluation of oxidation stability) in (test example 4) RBOT life-span
[condition 1]
According to the method for regulation in JIS K 2514-1996, use rotating missile oxidation test instrument " RBOT-02 " (by clutch
Company manufactures) carry out oxidation stability test.Load in pressure vessel 49.50g mixed ester or ester (mixed ester 1～8, ester A or
Ester B), 0.25g 4,4 '-di-2-ethylhexylphosphine oxide (2,6-di-t-butyl phenol) (by Tokyo chemical conversion industrial group manufacture), 0.25g
IRGANOX L57 (being manufactured by Ciba Specialty Chemicals), 5mL water and use sand paper #400 polishing electrolysis copper cash (diameter: 1.6mm,
Length: 3m), and it is pressurized to 620 kPa with oxygen.Pressure vessel is placed in the temperature chamber at 150 DEG C, and rotates with 100 rpm
To start test.After the pressure of pressure vessel is reached maximum, pressure is reduced to the point of 175 kPa and is defined as terminal.Obtain from test
The time (RBOT life-span) started to terminal.Result is shown in Tables 1 and 2.In Tables 1 and 2, the longer RBOT life-span
(condition 1) shows, mixed ester or ester have preferable oxidation-hydrolytic stability.
[condition 2]
Carrying out in the same manner as described above operating (see " condition 1 "), difference is, does not use 4,4 '-methylene
Double (2,6-di-t-butyl phenol), IRGANOX L57 and water, and minute (RBOT life-span).Result is shown at table 1
With in table 2.In Tables 1 and 2, the longer RBOT life-span (condition 2) shows, mixed ester or ester have the oxidation-stabilized of excellence
Property.
The mensuration (evaluation of electrical insulation capability) of (test example 5) specific insulation
According in JIS C 2101-1999 regulation method, use numeral ultra-high resistance/microgalvanometer " R8340A " (by
ADVANTEST company manufacture) and fluid electrode " DAC-OBE-2 " (being manufactured by Zong Yan electric corporation) mensuration mixed ester 1～8 30
Specific insulation at DEG C.Result is illustrated below.
The mensuration of (test example 6) pour point
According in JIS K 2269-1987 regulation method, use automatic pour point measurement system " RPC-01CML " (by from
Conjunction company manufacture) measure mixed ester 1～8 pour point.Result is illustrated below.
The mensuration (evaluation of abrasion resistance properties) of (test example 7) grinding defect diameter
0.45g tricresyl phosphate (chemical conversion industrial group manufactures by Tokyo) is joined 14.55g mixed ester (mixed ester 1
～8 or mixed ester C) in prepare refrigerator oil.Use Xie Ershi (shell) four-ball tribotester (by Shen Gangzao machine company
Manufacture), refrigerator oil is carried out wear test (load: 100 N, rotary speed: 1200 rpm, persistent period: 60 minutes, temperature
Degree: 75 DEG C, testpieces (test ball (SUJ-2)), thus measure grinding defect diameter.By three fixing balls in the vertical and horizontal direction
The meansigma methods of grinding defect diameter be taken as grinding defect diameter.Result is illustrated below.Less grinding defect diameter shows, refrigerator oil has more
Good abrasion resistance properties.
(test example 8) weight reduces the mensuration (evaluation of heat stability) of temperature
It is to use TG-DTA analyser " Tg-DTA 6200 " (instrument company manufactures by Seiko) to survey under the following conditions
5% weight determining mixed ester 1～8 reduces temperature.Result is illustrated below.
Mensuration temperature: 40 DEG C～420 DEG C, heating rate: 10 DEG C/min, atmosphere: nitrogen stream (300mL/ minute), sample
Container: aluminium vessel (15 μ L (opening)), sample size: 3mg
Table 2
As shown in table 1, the mixed ester 1～8 kinematic viscosity at 40 DEG C is 60.0mm2/ s～108.4mm2/ s, with HFO-
Two-phase laminated flow temperature during 1234yf mixing is less than-17 DEG C, and mixes with HFO-1234ze/HFC-32 (weight ratio: 60/40)
Time two-phase laminated flow temperature be less than-15 DEG C；Solidification/precipitate is not shown at-20 DEG C；In 1 time RBOT life-span of condition it is
More than 2070 minutes；And it is more than 65 minutes in 2 times RBOT life-spans of condition.When mixed ester 2,4 and 8 mixes with HFO-1234ze
Two-phase laminated flow temperature be less than-50 DEG C.Thereby confirm that, mixed ester 1～8 balancedly have excellence with comprise the cold of fluoropropene
Freeze the compatibility of agent, excellent cryogenic property, excellent oxidation-hydrolytic stability and the oxidation stability of excellence, have simultaneously
Viscosity in the range of refrigerator oil is required.As shown in table 2, ester A has a poor cryogenic property, and ester B have poor with
The compatibility of HFO-1234yf and HFO-1234ze/HFC-32 (weight ratio: 60/40).Compared with mixed ester 1～8, ester A and ester B
Performance balance poor.
In test example 1, mixed ester C kinematic viscosity at 40 DEG C is 67.0mm2/ s, the kinematic viscosity at 100 DEG C
For 8.3mm2/ s, and viscosity index (VI) is 92.
In test example 5, the specific insulation (30 DEG C) of mixed ester 1～8 is 1 × 1016More than Ω cm.Thereby confirm that,
The mixed ester of the present invention has enough electrical insulation capabilities.
In test example 6, the pour point of mixed ester 1～8 is less than-37.5 DEG C.Thereby confirming that, the mixed ester of the present invention has
Enough low temperature flows.
In test example 7, the polishing scratch of the refrigerator oil being made up of mixed ester (mixed ester 1～8) and tricresyl phosphate is straight
Footpath is below 0.23mm.The grinding defect diameter of the refrigerator oil being made up of mixed ester C and tricresyl phosphate is 0.37mm.The most true
Recognizing, the mixed ester of the present invention provides excellent abrasion resistance properties to the refrigerator oil of the present invention.
In test example 8, it is more than 260 DEG C that 5% weight of mixed ester 1～8 reduces temperature.Thereby confirm that, the present invention's
Mixed ester has enough heat stability.
Industrial applicability
Therefore, the present invention provides a kind of mixed ester, described mixed ester balancedly show excellence performance (such as, with comprise
The compatibility of the cryogen of fluoropropene, cryogenic property, oxidation stability, oxidation-hydrolytic stability and lubricity), have simultaneously
Viscosity in the range of refrigerator oil is required, and can be in middle uses such as industrial lubricants (such as, refrigerator oil).
Claims (5)
1. a mixed ester for tetramethylolmethane or polyols blend and carboxylic acid, described polyols blend is by tetramethylolmethane with by following formula
(I) the dipentaerythritol composition represented, and described carboxylic acid comprises 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid, wherein 3,5,
The mol ratio of 5-tri-methyl hexanoic acid and 2-propylheptanoic acid in the range of 90/10～10/90,
Mixed ester the most according to claim 1, wherein said carboxylic acid by 3,5,5-tri-methyl hexanoic acids and 2-propylheptanoic acid group
Become.
Mixed ester the most according to claim 1 and 2, wherein said mixed ester be tetramethylolmethane with containing 3,5,5-trimethyls
The mixed ester of the carboxylic acid of caproic acid and 2-propylheptanoic acid.
4. a refrigerator oil, it comprises according to the mixed ester according to any one of claims 1 to 3.
5., for a working fluid composition for fridge, it comprises refrigerator oil according to claim 4 and freezing
Agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-019802 | 2012-02-01 | ||
| JP2012019802 | 2012-02-01 | ||
| PCT/JP2013/052137 WO2013115296A1 (en) | 2012-02-01 | 2013-01-31 | Mixed ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104254515A CN104254515A (en) | 2014-12-31 |
| CN104254515B true CN104254515B (en) | 2016-11-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400293A (en) * | 2001-07-31 | 2003-03-05 | 日本能源株式会社 | Cooling engine oil for hydrocarbon refrigerant |
| WO2008105366A1 (en) * | 2007-02-27 | 2008-09-04 | Nippon Oil Corporation | Refrigerator oil and working fluid composition for refrigerator |
| WO2010029704A1 (en) * | 2008-09-09 | 2010-03-18 | 株式会社ジャパンエナジー | Refrigerator oil for refrigerant 2,3,3,3-tetrafluoro-1-propene |
| WO2010050871A1 (en) * | 2008-10-27 | 2010-05-06 | Perstorp Specialty Chemicals Ab | Low pour point lubricant base stock |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400293A (en) * | 2001-07-31 | 2003-03-05 | 日本能源株式会社 | Cooling engine oil for hydrocarbon refrigerant |
| WO2008105366A1 (en) * | 2007-02-27 | 2008-09-04 | Nippon Oil Corporation | Refrigerator oil and working fluid composition for refrigerator |
| WO2010029704A1 (en) * | 2008-09-09 | 2010-03-18 | 株式会社ジャパンエナジー | Refrigerator oil for refrigerant 2,3,3,3-tetrafluoro-1-propene |
| WO2010050871A1 (en) * | 2008-10-27 | 2010-05-06 | Perstorp Specialty Chemicals Ab | Low pour point lubricant base stock |
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