compounds

Abstract

To provide a lubricant that can be used in conjunction with heat transfer fluids for use in refrigerant systems, the lubricant having a MW of 5500 or less and a polydispersity index of 1.45 or less.SOLUTION: The present invention relates to compounds according to formula (Ia) or formula (Ib), compositions comprising these compounds and methods for their production, wherein n is an integer of from 2 to 49, m is an integer of from 0 to 3, W is H, F, Cl, Br, I or (CY2)mCY3, Y is F, Cl, Br or I, Z is H, OH, (CW2)pCW3, CY3 or the like, with an average molecular weight (MW) of 5500 or less and a polydispersity index of 1.45 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to compounds, compositions, their uses, and methods for preparing them. The compounds of the present invention are halogenated polyethers. The compositions of the present invention include a heat transfer part and a lubricating part, and the lubricating part includes a halogenated polyether. The compositions of the present invention can be used in refrigerants and refrigerant mixtures. The compounds of the present invention can be prepared by polymerization of fluorinated epoxides. [Background technology]

[0002] The listing or discussion of a prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.

[0003] Fluorocarbon-based compounds are currently used in many commercial and industrial applications, for example as propellants, blowing agents, and heat transfer fluids. The need for new refrigerants has led to increased interest in and use of fluorinated compounds, particularly (hydro)fluoroolefins, as heat transfer fluids.

[0004] Dichlorodifluoromethane (refrigerant R-12) has a favorable combination of refrigeration properties and was the most widely used refrigerant for many years. International concern that fully and partially halogenated chlorofluorocarbons such as dichlorodifluoromethane and chlorodifluoromethane were damaging the Earth's protective ozone layer led to comprehensive agreements to severely restrict and eventually completely phase out their production and use. Use of dichlorodifluoromethane was phased out in the 1990s.

[0005] Chlorodifluoromethane (R-22) was introduced as an alternative to R-12 due to its low ozone depletion potential. Following concerns that R-22 is a strong greenhouse gas, its use is also being phased out. R-410A and R-407 (including R-407A, R-407B, and R-407C) were introduced as alternatives to R-22. However, R-22, R-410A, and R-407 refrigerants all have high Global Warming Potentials (GWP, also known as Greenhouse Warming Potential).

[0006] 1,1,1,2-tetrafluoroethane (refrigerant R-134a) has been introduced as an alternative refrigerant to R-12. However, despite its low ozone depletion potential, R-134a has a GWP of 1430. It would be desirable to find an alternative to R-134a with a lower GWP.

[0007] R-152a (1,1-difluoroethane) has been identified as a replacement for R-134a. It is somewhat more efficient than R-134a, with a greenhouse warming potential of 120. However, R-152a has been determined to be too flammable to be safely used, for example, in mobile air conditioning systems. In particular, its low temperature ignition limit in air is too low, its flame speed is too fast, and its ignition energy is too low.

[0008] R-410A is a non-flammable mixture of R-32 (difluoromethane) and R-125 (pentafluoroethane) in a 50% / 50% weight ratio. It is widely used as an air conditioning refrigerant, but has a GWP of 2107. It is desirable to find an alternative to R-410A that has a lower GWP.

[0009] R-32 has been proposed as a low GWP replacement for R-410A, but is flammable. Furthermore, R-32 may exhibit regions of liquid-liquid immiscibility when combined with polyol ester (POE) refrigeration lubricants. R-32 has a higher solubility in POE lubricants than R-410A, which also has the potential to reduce the effective viscosity of the lubricant phase. This may lead system designers to recommend higher viscosity grades of lubricants for use with R-32 over R-410A, which may reduce compressor efficiency. It would therefore be desirable to find combinations of R-32 and lubricants that reduce flammability, improve mutual miscibility, and / or provide acceptable solubility of the refrigerant in the lubricant (and of the lubricant in the refrigerant).

[0010] Carbon dioxide (R-744) is increasingly being used as a refrigerant in stationary and mobile air conditioning and refrigeration applications. Carbon dioxide is used in conjunction with polyalkylene glycol (PAG) lubricants. Traditional PAG lubricants exhibit a wide liquid immiscibility region with R-744, which can cause heat transfer problems in the evaporators of systems using this type of heat transfer composition. It would be advantageous to identify lubricants with improved miscibility with R-744 and heat transfer compositions that have improved combinations with R-744.

[0011] PAG lubricants also exhibit hygroscopic properties, which in systems using R-744 can lead to the formation of carbonic acid and therefore corrosion in the system. It would be advantageous to find a heat transfer composition including R-744 that has reduced hygroscopic properties.

[0012] (Hydro)fluoroolefins, particularly tetrafluoropropene, have been proposed as potential refrigerants for use in various heat transfer devices.

[0013] Heat transfer fluids are often used in combination with lubricants, such as in heating and refrigeration systems. Such lubricants are included in the heat transfer composition to ensure the continued smooth operation of the mechanical components of the heat transfer system.

[0014] Lubricants used in heat transfer compositions must be compatible with the refrigerant in the composition. Compatibility between the lubricant and the refrigerant is contemplated by a number of factors, including the desire for at least partial miscibility over a portion of the operating temperature range, low tendency to degrade or react during use, and suitable viscosity for the application.

[0015] However, in much of the prior art relating to the polymerization and polymerization of trifluoropropylene oxide, it is clear that the processes used, and the products produced by these processes, are not suitable for use in lubricating and heat transfer compositions having refrigerants and refrigerant mixtures containing (hydro)fluoroolefins.

[0016] Polymers produced by these methods often produce solid or very viscous polymers with molecular weights in excess of 50,000.

[0017] WO2017 / 098238 describes a composition comprising a heat transfer portion and a lubricating portion, the lubricating portion comprising a halogenated polyether. The method of polymerizing fluorinated epoxides described in WO2017 / 098238 may not be ideal for industrial scale development. DISCLOSURE OF THEINVENTION

[0018] Thus, there is a need for lubricants that can be used in combination with heat transfer fluids for use in refrigeration systems. To match these requirements, lubricants with M below 5500 are required. W And lubricants having a polydispersity index of 1.45 or less are preferred.

[0019] Thus, there is a need for lubricants that can be used in combination with heat transfer fluids, both those currently in use and those proposed as alternative compositions. In particular, lubricants that are miscible with a wide range of heat transfer fluids, have suitable viscosities, do not degrade the performance of the heat transfer fluids, and have low flammability, in addition to functioning successfully as lubricants, are desirable.

[0020] Additionally, there is a need for methods that can produce such polymers without the need for hazardous initiators and / or solvents, and / or that can reduce reaction times from days to hours, and / or that allow better control over the properties of the produced polymer.

[0021] Low flammability lubricants are particularly important for heat transfer fluids used in air conditioning applications, such as vehicle air conditioning, due to the risk of such compositions coming into contact with hot metal surfaces in the engine. Similarly, in stationary residential air conditioning applications, the air conditioning units are often located near the building's furnaces, and the use of flammable refrigerants in this application poses the risk of the heat transfer composition coming into contact with hot furnace surfaces.

[0022] The present invention relates to a compound represented by formula (Ia) or (Ib), [ka] During the ceremony, Each W is independently selected from H, F, Cl, Br, I and (CY 2)m CY3, each Y is independently selected from the group consisting of F, Cl, Br, and I; Each Z is independently H, OH, (CW2) p CW3, CY3, OCW3, O(CW2) p CW3, (CW2) p OH, polyalkylene glycol, and polyol ester, n is an integer from 2 to 49; m is an integer from 0 to 3; p is an integer from 0 to 9; Molecular weight average (M W ) is less than or equal to 5500, These and other deficiencies are addressed by providing compounds having a polydispersity index of 1.45 or less.

[0023] for example, each W is independently selected from the group consisting of H, F, Cl, Br, and I; each Y is independently selected from the group consisting of F, Cl, Br, and I; Each Z is independently H, OH, (CW2) p CW3, CY3, OCW3, O(CW2) p CW3, polyalkylene glycols and polyol esters; n is an integer from 2 to 49; m is an integer from 0 to 3; p is an integer from 0 to 9; Molecular weight average (M W ) is less than or equal to 5500, The polydispersity index is less than or equal to 1.45.

[0024] For example, at least one (CY2) m CY3 may be CF3 (ie, m=0 and each Y is F).

[0025] For example, (CY2) M CY3 may be CF3 and at least one W may also be (CY2) m Specifically, each (CY 2)M The CY3 group may be CF3.

[0026] Examples of compounds of formula Ia and Ib include (CY2) m Included are compounds where CY3 is CF3, one W is CF3, and each W group is H. Further examples include compounds where (CY2) m CY3 is CF3 、 Included are compounds in which one or two W groups are F and one or two W groups are H (eg, two W groups are H and one W group is F).

[0027] Each repeat unit of the compound of the present invention has two groups (CY2) m When CY3 contains, for example, two CF3 groups, these may be attached to the same carbon atom or to adjacent carbon atoms in the chain or backbone.

[0028] Alternatively, the compound of formula (Ib) can be represented by the following formula (Ic): [ka]

[0029] The compounds of formula (Ia), (Ib) and (Ic) have an M of 4000 or less, preferably 3000 or less, more preferably 2500 or less. W may have:

[0030] The compounds of formula (Ia), (Ib) and (Ic) may have a polydispersity index of about 1.45, preferably about 1.35, more preferably about 1.30, and even more preferably about 1.25.

[0031] Y is preferably F or Cl, and more preferably Y is F.

[0032] W is preferably H, F or Cl. More preferably, W is H.

[0033] Advantageously, m is an integer between 0 and 3, preferably 0.

[0034] n is preferably an integer of 2 to 49, for example, an integer of 5 to 25, and preferably, n is an integer of 6 to 20, for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0035] It will be understood that a reference to formula (I) refers to formula (Ia), formula (Ib) and / or formula (Ic).

[0036] In some compounds of formula (I), at least one, and possibly both, of the Z derivatives is not H or OH.

[0037] In some compounds of formula (I), at least one Z derivative may include a polyalkylene glycol. Alternatively, both Z derivatives may include a polyalkylene glycol (PAG). In both cases, the polyalkylene glycol may be selected from the group consisting of poly(ethylene) oxide, poly(propylene) oxide, and mixtures thereof. In such embodiments, the PAG group may be attached to the compound of formula (I) via the formation of an ester bond between the hydroxyl end-capping group of formula (I) (i.e., Z=OH or Z=(CW2)) and the carboxylic acid end-capped PAG.

[0038] In some compounds of formula (I), at least one Z derivative may comprise a fluorinated PAG (F-PAG). The F-PAG may be selected from the group consisting of F3C-end-capped PAGs and hydroxyl-end-capped PAGs.

[0039] The hydroxyl end groups of the F-PAGs can provide further scope for derivatization and can, for example, be converted to ether or ester groups, which can be aliphatic, aromatic, linear, branched, fluorine-containing, or otherwise functionalized to further tune the properties of the product.

[0040] The present inventors have found that the lubricating properties of compounds of formula (I) may be improved when at least one Z derivative comprises an F-PAG.

[0041] In some compounds of formula (I), the Z derivatives may independently be alkyl or alkoxy groups containing from 1 to 10 carbon atoms.

[0042] Both Z derivatives may be the same, or alternatively, both Z derivatives may be different.

[0043] p is preferably an integer of 1 to 6, more preferably 2 to 6, for example, 3 to 5.

[0044] The compound of formula (I) may have, for example, a viscosity of about 5 to about 250 cP at 40° C. The compound of formula (I) may have a viscosity of about 15 to about 150 cP at 40° C.

[0045] The compound of formula (Ia) may be a compound of formula (IIa). [ka]

[0046] The compound of formula (Ib) may be a compound of formula (IIb). [ka]

[0047] Alternatively, or in addition, the compound of formula (Ia) may be a compound of formula (IIIa). [ka]

[0048] Alternatively, or in addition, the compound of formula (Ib) may be a compound of formula (IIIb). [ka]

[0049] Those skilled in the art will appreciate that the above formula is merely representative and that structural defects in the polymer chains may exist.

[0050] The composition may, for example, comprise at least two different compounds of formula (I). In such a case, the value of n may be the same for at least two compounds of formula (I). Alternatively, the value of n may be different for at least two compounds of formula (I).

[0051] Preferably, the compound of formula I is a compound of formula (IB).

[0052] The compound of formula (I) may be a mixture of compounds of formula (Ia) and (Ib). In this situation, it is preferred that the majority of the mixture is the compound of formula (Ib), for example more than 50% by weight of the mixture is the compound of formula (Ib), preferably more than 75%, more preferably more than 90% or 95% is the compound of formula (Ib).

[0053] Compounds of formula (I) may be prepared by a process involving the polymerization of an epoxide precursor.

[0054] The epoxide precursor preferably has the formula (IV): [ka] During the ceremony, R1 is (CY2) m It's CY3, R2 is H, F, Cl, Br, I or (CY2) m It's CY3, R3 is H, F, Cl, Br, I or (CY2) m It's CY3, R4 is H, F, Cl, Br, I or (CY2) m It's CY3.

[0055] for example, R1 is CF3, R2 is H, F or CF3; R3 is H, F or CF3; R4 is H or CF3.

[0056] for example, R1 is CF3, R2 is H or F; R3 is H or F; R4 is 、 H or CF3.

[0057] Examples of epoxide precursors that may be used include epoxides according to formula (IV) where R1 is CF3, R2 is H, R3 is H, and R4 is H (epoxide of 3,3,3-trifluoropropene (1243zf)), epoxides according to formula (IV) where R1 is CF3, R2 is F, R3 is H, and R4 is H (epoxide of 2,3,3,3-tetrafluoropropene (1234yf)), epoxides according to formula (IV) where R1 is CF3, R2 is H, R3 is F, and R4 is H (epoxide of 1,3,3,3-tetrafluoropropene (1234ze)), epoxides according to formula (IV) where R1 is CF3, R2 is H, R3 is F, and R4 is H (epoxide of 1,3,3,3-tetrafluoropropene (1234ze)), These include epoxides where R1 is CF3, R2 is H, R3 is CF3, and R4 is H, epoxides where R1 is CF3, R2 is H, R3 is H, and R4 is CF3 (epoxide of 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz)), and epoxides where R1 is CF3, R2 is CF3, R3 is H, and R4 is H (epoxide 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propene oxide (HFIBO)). Preferably, the epoxide is the epoxide of 1243zf (1,1,1-trifluoro-2,3-epoxypropane).

[0058] The method may involve the polymerization of an epoxide using an initiator formed from a base and an alcohol.

[0059] Preferably, the base is a Group I or Group II metal hydroxide, more preferably a Group I metal hydroxide, even more preferably sodium hydroxide or potassium hydroxide, even more preferably potassium hydroxide.

[0060] Preferably, the alcohol is a primary alcohol. The primary alcohol is, for example, a C1-C 10 The primary alcohol may be, for example, a C1-C 10 The primary alcohol may be, for example, a fluorinated alcohol, for example, a C1-C 10The fluorinated alcohol may be of the formula (I), preferably trifluoroethanol.

[0061] The polymerization of the epoxide can be carried out in the absence of a solvent.

[0062] The polymerization reaction can be carried out at a temperature of about 0 to about 130°C, preferably about 40 to about 100°C, and more preferably about 50 to about 90°C.

[0063] The polymerization reaction can be carried out at a pressure of about 100 to about 1000.3 kPa, preferably about 101 kPa.

[0064] The compounds of formula (I) may be used as lubricants.

[0065] The compound of formula (I) may form part of a composition, the compound of formula (I) being the lubricating portion and the composition also including a heat transfer portion. Preferably, the composition includes a single liquid phase over the entire temperature range between -30°C and 70°C.

[0066] The weight percentage of the lubricating portion in the total composition of the present invention can be, for example, about 1 to about 30%, preferably about 1 to about 10%, and more preferably about 1 to about 5%.

[0067] The heat transfer portion may comprise one or more compounds selected from the group consisting of (hydro)fluoroolefins (HFOs), hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), perfluoroalkyl iodides and hydrocarbons.

[0068] The heat transfer portion may be, for example, 1,1,2,3,3,3-pentafluoropropene (R-1225ye), 1,3,3,3-tetrafluoropropene (R-1234ze), 2,3,3,3-tetrafluoropropene (R-1234yf), 3,3,3-trifluoropropene (R-1243zf), 1,1,1,2-tetrafluoroethane (R-134a), 1,1-difluoroethane (R-152a), difluoromethane (R-32), fluoroethane (R-161), pentafluoroethane (R-125), 1,1,2,2-tetrafluoroethane (R-134), propane, propylene, carbon dioxide, 1,1,1,3,3-pentafluoropropane (R-245fa), 1,1,1,3,3,3-hexofluoropropane (R-236fa), 1,1,1, 2,2-Pentafluoropropane (R-245cb), 1,1,1,2,3,3,3-Heptafluoropropane (R-227ea), 1,1,1-Trifluoroethane (R-143a), n-butane, isobutane, and 1,1,1,3,3-Pentafluorobutane (R-365mfc), 1,1,2-Trifluoroethylene (R-1123), 1,1-Difluoroethylene (R The present invention includes one or more compounds selected from the group consisting of: R-1132a), trifluoromethyl iodide (CF3I), carbon dioxide (R-744), ethane (R-170), ethylene (R-1150), propene (R-1270), propane (R-290), isobutane (R-600a), n-butane (R-600), n-pentane (R-601) and isopentane (R-601a).

[0069] For the avoidance of doubt, where a compound can exist as one of two conformational isomers around a double bond, e.g., cis and trans isomers, the use of a term without an isomer designation (e.g., R-1234ze) will be understood to refer to either isomer.

[0070] The heat transfer portion may comprise tetrafluoropropene. Preferably, the heat transfer portion comprises R-1234ze, and even more preferably, the heat transfer portion comprises R-1234ze(E).

[0071] The heat transfer composition may include R-1234yf.

[0072] The heat transfer composition may include CF3I.

[0073] The heat transfer composition may include R-32.

[0074] The heat transfer composition may include R-32 and R-1234yf.

[0075] The heat transfer composition may include R-1132a, R-1123, or a combination of one or more of these with R-32.

[0076] The heat transfer composition may include a hydrocarbon selected from R-170, R-1150, R-1270, R-290, R-600a, R-600, R-601, and R-601a.

[0077] The heat transfer composition may include R-744.

[0078] Some compositions of the present invention are less flammable than compositions containing the same heat transfer moieties in combination with polyalkylene glycol (PAG) and / or polyol ester (POE) based lubricants.

[0079] The compositions of the present invention may be miscible with existing polyalkylene glycol, polyalkylene glycol ester, and polyol ester lubricating oils.

[0080] The compound comprising the lubricating moiety typically comprises carbon, hydrogen, and oxygen, the ratio of oxygen to carbon being sufficient to provide some degree of miscibility with the heat transfer moiety, such as when the lubricating moiety is added to the heat transfer moiety at a ratio of about 1-30% by weight, preferably 1-10% by weight, and even more preferably 1-5% by weight, of the total composition, and the mixture has one liquid phase. Preferably, the mixture has one liquid phase when 1-20% by weight of the lubricating moiety is present in the composition. Even more preferably, the composition is one liquid phase, regardless of the ratio of the heat transfer moiety to the lubricating moiety. This solubility or miscibility is preferably present at all normal operating temperatures. For example, the solubility or miscibility is present at at least one temperature between -100°C and +100°C, preferably at least one temperature between -75°C and +75°C, and even more preferably at least one temperature between -50°C and +50°C. Advantageously, the solubility or miscibility is present over the entire temperature range in which the composition is in a liquid phase.

[0081] Advantageously, the compositions of the present invention (comprising a compound of formula (I) and a heat transfer compound or moiety) are less flammable than the heat transfer compound or moiety alone.

[0082] Preferably, the compositions of the present invention have a minimum ignition temperature of about 500°C or higher, e.g., about 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, or 590°C, preferably about 600°C or higher, e.g., about 610°C, 620°C, 630°C, or 640°C.

[0083] Advantageously, the compositions of the present invention have reduced moisture absorption compared to heat transfer compositions containing non-halogenated PAG or polyether lubricants.

[0084] The compositions of the present invention may be non-flammable.

[0085] Flammability may be determined according to ASHRAE Standard 34, which incorporates ASTM Standard E-681 using the test methodology per appendix p. 34, dated 2004, the entire contents of which are incorporated herein by reference.

[0086] Advantageously, the Global Warming Potential (GWP) of the compositions of the present invention may be less than about 3500, 3000, 2500 or 2000. For example, the GWP may be less than 2500, 2400, 2300, 2200, 2100, 2000, 1900, 1800, 1700, 1600 or 1500. The GWP of the compositions of the present invention is preferably less than 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600 or 500.

[0087] The compositions of the present invention have an ozone depletion potential of zero or near zero.

[0088] The compositions of the present invention may have improved heat transfer properties over the heat transfer fluid alone.

[0089] Without wishing to be bound by theory, it is believed that compounds of formula (I) may further act as heat transfer agents and thus improve the heat transfer properties of the compositions of the present invention.

[0090] The composition may optionally include a stabilizer, preferably the stabilizer is selected from diene-based compounds, phosphates, phenolic compounds and epoxides, and mixtures thereof.

[0091] The composition may optionally contain a flame retardant. Advantageously, the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl)phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, fluorinated iodocarbons, fluorinated bromocarbons, trifluoroiodomethane, perfluoroalkylamines, bromofluoroalkylamines, and mixtures thereof.

[0092] The composition may also include an anti-wear additive, such as tricresyl phosphate.

[0093] The composition of the present invention may be contained in the lubricant composition in a proportion of at least about 10 to about 90% by weight, preferably about 10 to about 75% by weight, for example, about 10, 20, 30, 40 or 50% by weight.

[0094] The present invention also provides a heat transfer device comprising the composition of the present invention and / or the use of the composition of the present invention in a heat transfer device.

[0095] The heat transfer device may be, for example, a refrigeration device.

[0096] For example, the heat transfer device may be selected from the group consisting of an automotive air conditioning system, a residential air conditioning system, a commercial air conditioning system, a residential refrigerator system, a residential refrigeration system, a commercial refrigerator system, a commercial refrigeration system, a chiller air conditioning system, a chiller refrigeration system, and a commercial or residential heat pump system.

[0097] Preferably, the heat transfer device comprises a compressor.

[0098] According to one aspect of the invention, there is provided a method of cooling an article, the method comprising condensing a composition of the invention and then evaporating the composition in the vicinity of the article to be cooled.

[0099] According to a further aspect of the invention, there is provided a method of heating an article comprising condensing a composition of the invention in the vicinity of the article to be heated and thereafter evaporating the composition.

[0100] According to a further aspect of the present invention there is provided a mechanical power generating device comprising the composition of the present invention.

[0101] Preferably, the mechanical power generation device is adapted to generate work from heat using a Rankine cycle or a modification thereof.

[0102] Also provided is a method of retrofitting a heat transfer device, the method comprising removing an existing heat transfer fluid and introducing a composition of the present invention. Preferably, the heat transfer device is a refrigeration device. Preferably, the heat transfer device is an air conditioning system.

[0103] There is also provided a method for reducing the flammability of a composition by adding the composition of the present invention.

[0104] The compositions of the present invention that include a heat transfer moiety can be prepared, for example, by mixing one or more compounds of formula (I) with a heat transfer fluid.

[0105] In one aspect of the present invention, the composition can be used as a heat transfer agent. When used as a heat transfer agent, the composition of the present invention can optionally comprise at least two compounds according to formula (I).

[0106] In another embodiment, the composition of the present invention can be used as a lubricant. In a further embodiment, the lubricant composition can comprise at least two compounds according to formula (I).

[0107] The use of an effective amount of the compounds according to formula (I) in lubricant or heat transfer compositions is advantageous for their thermal and mechanical stability, lubricity, viscosity, pour point, antioxidant and anticorrosion properties. [Brief description of the drawings]

[0108] [Figure 1] FIG. 1 is a graph showing the viscosity-temperature profiles of reference oil Supercool PAG 46 (a commercial PAG refrigerated lubricant) and Example 5-F (F). [Diagram 2] Gel permeation chromatography (GPC) analysis of Supercool PAG 46. [Diagram 3] GPC analysis of Example 5-F(F). [Figure 4] 1 is vapor-liquid equilibrium data for R-1234yf and Example 5-F(F). [Diagram 5]1 is vapor-liquid equilibrium data for R-1234yf and Supercool PAG 46 reference oil. EXAMPLES

[0109] The invention is illustrated by the following non-limiting examples.

[0110] The compounds according to the present invention were synthesized by the following method.

[0111] Common methods: The initiator mixture was prepared by adding an amount of base (e.g., 85-86% KOH) along with 2-3 drops of Aliquat 336 to an alcohol (e.g., ethylene glycol or trifluoroethanol) in a Pyrex round-bottom flask with stirring and cooling. When the base was dissolved in the alcohol, the reaction flask was fitted with a dropping funnel and a condenser before adding the epoxide monomer (e.g., 3,3,3-trifluoro-1,2-epoxypropane). The mixture was then heated with stirring for a period of time. At the end of the reaction, the product was cooled and dissolved in a minimum amount of chloroform (e.g., 250 ml). This chloroform solution was washed with acidic water (e.g., 4 g of 36% HCl in 100 ml of water) and then washed three times with water only (e.g., 100 ml). The washed chloroform solution of the polymer product was dried over anhydrous sodium sulfate and, after filtration, the solvent was removed by distillation under reduced pressure.

[0112] The resulting polymer products were analyzed and characterized by the following: Gel permeation chromatography (GPC): GPC was performed on a Shimadzu Prominence LC system equipped with a RI detector equipped with a 300 mm × 75 mm, 5 μm PLgel 100 Å and a 300 mm × 7.5 mm, 5 μm PLgel 500 Å column in series with a THF eluent at 1.0 ml / min. The method was calibrated with poly(styrene) standards with MWs ranging from 1000 to 10000.

[0113] Viscosity measurements: Viscosity measurements were performed on a TA Instruments Discovery Hybrid Rheometer at 10 rad / s between -20 and 70 °C using a 40 mm 2.008° cone-plate geometry.

[0114] Using this general methodology, a series of polymer products were produced. Details of each formulation and the main properties of each product are outlined in Table 1, which also includes data for a reference example, the commercial refrigeration lubricant Supercool PAG 46. [Table 1]

[0115] The results are shown to be comparable to a reference (Supercool PAG 46, a commercially available PAG refrigeration lubricant) using the method of the present invention. 、 Molecular weight control (M W and M. n It clearly shows that the polymer can be simply and easily produced with significant improvement in polydispersity index (PDI) and the product of Example 5-F(F) has particularly good properties, and the viscosity measurement and GPC results of Reference Example and Example 5-F(F) are shown in Figures 1-3.

[0116] Vapor liquid equilibrium (VLE) Vapor-liquid equilibrium data were measured in a static constant volume apparatus consisting of a vessel of precisely known internal volume placed within a temperature-controlled metal block. A magnetic stirring device was placed inside the heated vessel. A heat transfer fluid, controlled at a constant temperature, was passed through the block, allowing the temperature inside the vessel to be precisely controlled. The cell was evacuated and then filled with known amounts of each component. The temperature of the cell was then changed in steps from approximately -30°C to +70°C. At each temperature, the cell temperature and pressure were recorded continuously and when steady conditions were reached.

[0117] Vapor-liquid equilibrium data was measured for R-1234yf and the product of Example 5-F(F), as shown in Figure 4. The system exhibits a positive deviation from ideal behavior, and the raw experimental data indicates that there is no region of liquid-liquid immiscibility over the temperature and composition range investigated.

[0118] Vapor-liquid equilibrium data was measured for R-1234yf and Supercool PAG 46, as shown in Figure 5. The data indicate that regions of liquid-liquid immiscibility may exist for mixtures with compositions of 60 wt / wt% R-1234yf and above. For mixtures with less than 50 wt / wt% R-1234yf, immiscibility is not expected over the temperature range investigated.

[0119] The results show that the product of Example 5-F(F) is miscible with R-1234yf in all ratios. The same miscibility is not observed with a commercial PAG refrigeration lubricant (Supercool PAG 46) and R-1234yf. Thus, the product of Example 5-F(F) exhibits superior properties to the commercial lubricant.

[0120] Example 6 Polymerizations involving 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (HFIBO): [ka]

[0121] The initiator mixture was prepared by dissolving potassium hydroxide (85%, 0.27 g) in trifluoroethanol (1.25 g) containing 2 drops of Aliquat 336 in a round bottom flask. The mixture was stirred under cooling until all the KOH pellets were dissolved. Once dissolved, the flask was transferred to a hot plate equipped with a condenser and 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (16.25 g) was added via a dropping funnel. The hot plate was then heated to 70° C. and the mixture began to reflux at 40° C. After refluxing for 24 hours, a viscous polymer had formed and the temperature of the reaction mixture was 60° C. After cooling and washing, the polymer was found to be soluble in tetrahydrofuran and 19 Analysis by F NMR spectroscopy showed several very broad signals characteristic of the polymer at -74.28, -75.08, -76.69, and -78.79 ppm (relative to perfluorobenzene at -164.9 ppm). Evaporation of the solvent gave a viscous white polymer.

[0122] Example 7 Polymerization with 75% TFPO and 25% HFIBO: The initiator mixture was prepared by dissolving potassium hydroxide (85%, 0.26 g) in trifluoroethanol (1.25 g) containing 2 drops of Aliquat 336 in a round bottom flask. The mixture was stirred under cooling until all the KOH pellets were dissolved. Once dissolved, the flask was transferred to a hot plate and 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (5.63 g) and TFPO (10.5 g) were added via a dropping funnel. The hot plate was then heated to 70 °C and the mixture began to reflux at 40 °C in the flask with a condenser supplied with a chiller. After refluxing for 24 hours, the polymer was formed and the temperature of the reaction mixture was 65 °C. After cooling, the polymer was washed and dissolved in tetrahydrofuran after an attempt to dissolve it with chloroform, and this layer was washed and dissolved in tetrahydrofuran. 19Analysis by FNMR spectroscopy showed several very broad signals characteristic of the polymer at -73.61, -74.14, -75.89, -77.17, and -79.32 ppm (relative to perfluorobenzene at -164.9 ppm). Evaporation of the solvent gave a grey polymer.

[0123] Comparative Example Comparative examples were carried out using a commercial PAG refrigeration lubricant (Supercool PAG 46) and the method and products of Example 1 of WO2017 / 098238.

[0124] The results clearly show that the molecular weight control and polydispersity index were significantly improved when ethylene glycol or trifluoroethanol and potassium hydroxide initiators were used in the absence of solvent, see Table 2. [Table 2]

[0125] Example 5 - Preparation of F(F) and Product Development Using the above procedure, a series of variations of the product of Example 5-F(F) were prepared by varying the composition of the initiator mixture. Details of the individual preparations and results are shown in Table 3.

[0126] In these examples, the number of repeat units, n, of the polymer products was estimated by GPC, and it was shown that polymers could be produced with n in the range of about 6 to 34.

[0127] Lubricating properties of polymers The lubrication properties of the polymer products from the Method and Product Development Examples were determined by measuring the coefficient of friction between a rotating ball bearing and three fixed ball bearings at various sliding speeds at 25°C as a function of axial force using a TA Instruments Discovery Hybrid Rheometer. See Table 4.

[0128] The results confirm that the polymers of the present invention are excellent lubricants comparable to Supercool PAG 46, a fully formulated commercial lubricant that incorporates additives designed to enhance lubricity. [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9]

Claims

1. A compound of formula (Ia) or (Ib), 【Chemistry 1】 During the ceremony, Each W is independently H, F, Cl, Br, I, and (CY ２ ) ｍ C.Y. ３ is selected from the group consisting of each Y is independently selected from the group consisting of F, Cl, Br, and I; Each Z is independently H, OH, (CW ２ ) ｐ C.W. ３ , C.Y. ３ , O.C.W. ３ , O(C.W. ２ ) ｐ C.W. ３ , O.C.W. ((C.Y. ２ ) ｍ C.Y. ３ ) C.W.C.W. ２ , (C.W. ２ ) ｐ OH, polyalkylene glycols and polyol esters; n is an integer from 2 to 49; m is an integer from 0 to 3; p is an integer from 0 to 9; Average molecular weight (M Ｗ ) is 5500 or less, A compound having a density dispersibility index of 1.45 or less.

2. each W is independently selected from the group consisting of H, F, Cl, Br, and I; each Y is independently selected from the group consisting of F, Cl, Br, and I; Each Z is independently H, OH, (CW ２ ) ｐ C.W. ３ , C.Y. ３ , O.C.W. ３ , O(C.W. ２ ) ｐ C.W. ３ , O.C.W. ((C.Y. ２ ) ｍ C.Y. ３ ) C.W.C.W. ２ , polyalkylene glycols and polyol esters; n is an integer from 2 to 49; m is an integer from 0 to 3; p is an integer from 0 to 9; The molecular weight average (M Ｗ ) is 5500 or less, 2. The compound of claim 1, wherein the polydispersity index is 1.45 or less.

3. Said M Ｗ 3. The compound according to claim 1 or 2, wherein M is 4000 or less, preferably 3000 or less, even more preferably 2500 or less.

4. The compound according to any one of claims 1 to 3, wherein said polydispersity index is about 1.40, preferably about 1.35, more preferably about 1.30, even more preferably about 1.

25.

5. A compound according to any one of claims 1 to 4, wherein Y is F or Cl, and preferably F, and / or W is H, F or Cl, and preferably H.

6. One W group is (CY ２ ) ｍ C.Y. ３ and two W groups are H, Y is F, and m is 0.

7. The compound of any one of claims 1 to 4, wherein one or two W groups are F, one or two W groups are H, Y is F, and m is 0.

8. 8. The compound of claim 7, wherein one W group is F, two W groups are H, Y is F, and m is 0.

9. 9. The compound of any one of claims 1 to 8, wherein Z comprises a polyalkylene glycol, optionally wherein the polyalkylene glycol is selected from the group consisting of poly(ethylene oxide) and poly(propylene oxide), and mixtures thereof.

10. A compound according to any one of claims 1 to 9, wherein at least one of the Z derivatives is not H or OH.

11. At least one of the Z derivatives comprises a fluorinated PAG (F-PAG), preferably the F-PAG is F ３ The compound of any one of claims 1 to 10, which is selected from the group consisting of C-terminally capped PAGs and hydroxyl-terminally capped PAGs.

12. A compound according to any one of claims 1 to 11, wherein n is an integer from 2 to 25, and / or m is 0, and / or p is 1 to 6, preferably 2 to 6, for example 3 to 5.

13. 13. The compound of any one of claims 1 to 12, having a viscosity of about 5 to about 250 cP at 40°C, optionally said viscosity being about 15 to 150 cP.

14. A composition comprising at least two different compounds of formula (Ia) and / or (Ib).

15. A composition comprising one or more compounds of formula (Ia) and / or (Ib) as defined in any one of claims 1 to 14 and a heat transfer moiety.

16. The composition according to claim 14 or 15, wherein the weight percentage of said compound(s) of formula (Ia) and / or (Ib) in said composition is 1 to 30% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

17. 17. The composition of claim 15 or 16, wherein the heat transfer portion comprises one or more compounds selected from the group consisting of (hydro)fluoroolefins (HFOs), hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), perfluoroalkyl iodides and hydrocarbons.

18. The heat transfer portion is made of R-32, R-152a, CF ３ 18. The composition of any one of claims 15 to 17, comprising R-1, R-1234ze, R-1234yf, R-1132a, R-1123, R-744, R-290 and / or R-600a.

19. 19. The composition of any one of claims 14 to 18, further comprising a stabilizer, optionally wherein said stabilizer is selected from diene-based compounds, phosphates, phenolic compounds and epoxides, and mixtures thereof.

20. 20. The composition of any one of claims 15 to 19, comprising a single liquid phase over the entire temperature range between -30°C and 70°C.

21. A process for the preparation of the compounds of formula (Ia) and / or formula (Ib) according to any one of claims 1 to 13, comprising the polymerization of an epoxide using an initiator formed from a base and an alcohol.

22. 22. The process according to claim 21, wherein the base is a Group I or Group II metal hydroxide, preferably sodium hydroxide or potassium hydroxide, more preferably potassium hydroxide.

23. 23. The method according to claim 22, wherein the alcohol is a primary alcohol, preferably ethylene glycol or trifluoroethanol.

24. 24. The process according to any one of claims 21 to 23, comprising said polymerization of an epoxide in the absence of a solvent.

25. The process according to any one of claims 21 to 24, wherein the reaction is carried out at a temperature of from about 0 to about 130°C, preferably from about 40 to about 100°C, more preferably from about 50 to about 90°C.

26. 26. The process according to any one of claims 21 to 25, wherein the reaction is carried out at a pressure of about 100 to about 1000.3 kPa, preferably about 101 kPa.

27. 27. The process according to any one of claims 21 to 26, wherein the polymerization is of an epoxide of any one of 3,3,3-trifluoropropene (1243zf), 2,3,3,3-tetrafluoropropene (1234yf), 1,3,3,3-tetrafluoropropene (1234ze), 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz) and hexafluoroisobutylene (HFIB), preferably of 1243zf (1,1,1-trifluoro-2,3-epoxypropane).

28. Use of a compound or composition as defined in any one of claims 1 to 20 in a heat transfer device, preferably wherein said heat transfer device is a refrigeration device.

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