COMPOUNDS

Abstract

The present invention relates to compounds according to formula (Ia) or formula (Ib);

##STR00001##

wherein each W is independently selected from the group consisting of H, F, Cl, Br, I and (CY.sub.2).sub.mCY.sub.3; each Y is independently selected from the group consisting of F, Cl, Br and I; each Z is independently selected from the group consisting of H, OH, (CW.sub.2).sub.pCW.sub.3, CY.sub.3, OCW.sub.3, O(CW.sub.2).sub.pCW.sub.3, OCW((CY.sub.2).sub.mCY.sub.3)CWCW.sub.2, (CW.sub.2).sub.pOH, polyalkylene glycol and polyolester; 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.sub.W) is ≤5500; and the polydispersity index is ≤1.45; compositions comprising these compounds and methods for their production.

Claims

1. A compound according to formula (Ia) or formula (Ib); ##STR00010## wherein each W is independently selected from the group consisting of H, F, Cl, Br, I, and (CY2)mCY3; each Y is independently selected from the group consisting of F, Cl, Br, and I; each Z is independently selected from the group consisting of H, OH, (CW2)pCW3, CY3, OCW3, O(CW2)pCW3, OCW((CY2)mCY3)CWCW2, (CW2)pOH, polyalkylene glycol, and polyolester; 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 (MW) is ≤5500; and the polydispersity index is ≤1.45.

2. A compound according to claim 1 wherein 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 selected from the group consisting of H, OH, (CW2)pCW3, CY3, OCW3, O(CW2)pCW3, OCW((CY2)mCY3)CWCW2, polyalkylene glycol, and polyolester; 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 (MW) is ≤5500; and the polydispersity index is ≤1.45.

3. A compound according to claim 1 wherein the MW is ≤4000.

4. A compound according to claim 1 wherein the polydispersity index is about 1.40.

5. A compound according to claim 1, wherein Y is F or Cl; and/or wherein W is H, F, or Cl.

6. A compound according to claim 1, wherein one W group is (CY2)mCY3, two W groups are H, Y is F, and m is 0.

7. A compound according to claim 1, wherein one or two W groups are F, one or two W groups are H, Y is F, and m is 0.

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

9. A compound according to claim 1, wherein Z comprises a polyalkylene glycol.

10. A compound according to claim 1, wherein at least one of the Z derivatives are not H or OH.

11. A compound according to claim 1, wherein at least one of the Z derivatives comprises a fluorinated-PAG (F-PAG).

12. A compound according to claim 1, wherein n is an integer from 2 to 25; and/or wherein m is 0; and/or wherein p is 1 to 6.

13. A compound according to claim 1 having a viscosity at 40° C. of from about 5 to about 250 cP.

14. A composition comprising at least two different compounds of formula (Ia) and/or (Ib) as defined in claim 1.

15. A composition comprising one or more compounds of formula (Ia) and/or (Ib) as defined in claim 1 and a heat transfer portion.

16. A composition according to claim 14, wherein the weight percentage of the compound or compounds of formula (Ia) and/or (Ib) in the composition is 1 to 30%.

17. A composition according to claim 15, 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. A composition according to claim 15, wherein the heat transfer portion comprises R-32, R-152a, CF3I, R-1234ze, R-1234yf, R-1132a, R-1123, R-744, R-290, and/or R-600a.

19. A composition according to claim 14, further comprising a stabiliser.

20. A composition according to claim 15, which comprises a single liquid phase across the entire temperature range between −30° C. and 70° C.

21. A method for making the compound of formula (Ia) and/or formula (Ib), according to claim 1, wherein the method comprises the polymerisation of an epoxide using an initiator formed from a base and an alcohol.

22. A method according to claim 21 wherein the base is a group I or group II metal hydroxide.

23. A method according to claim 22, wherein the alcohol is a primary alcohol.

24. A method according to claim 21, comprising the polymerisation of an epoxide in the absence of a solvent.

25. A method according to claim 21 wherein the reaction is carried out at a temperature of from about 0° C. to about 130° C.

26. A method according to claim 21 wherein the reaction is carried out at a pressure of from about 100 to about 1000.3 kPa.

27. A method according to claim 21 wherein the polymerisation is of an epoxide of any one of 3,3,3-trifluoropropene (1243zf), 2,3,3,3-tetrafluropropene (1234yf), 1,3,3,3-tetrafluoropropene (1234ze), 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz), and hexafluoroisobutylene (HFIB).

28. (canceled)

29. A heat transfer device comprising a composition according to claim 14.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0137] FIG. 1 is a graph showing the viscosity-temperature profile for the reference oil, Supercool PAG 46 (a commercial PAG refrigeration lubricant) and Example 5—F(F).

[0138] FIG. 2 is the Gel Permeation Chromatography (GPC) analysis of Supercool PAG 46.

[0139] FIG. 3 is the GPC analysis of Example 5—F(F).

[0140] FIG. 4 is the Vapour-Liquid Equilibria data for R-1234yf and Example 5—F(F).

[0141] FIG. 5 is the Vapour-Liquid Equilibria data for R-1234yf and Supercool PAG 46 reference oil.

EXAMPLES

[0142] The invention is illustrated by the following non-limiting examples.

[0143] Compounds according to the invention were synthesised by the following method.

[0144] General Method:

[0145] An initiator mixture was prepared by adding, with stirring and cooling, a quantity of base (e.g. 85-86% KOH) to an alcohol (e.g. ethylene glycol or trifluoroethanol) in a Pyrex round 25 bottomed flask along with 2-3 drops of Aliquat 336. When the base had dissolved in the alcohol the reaction flask was equipped with a dropping funnel and a condenser before the epoxide monomer (e.g. 3,3,3-trifluoro-1,2-epoxypropane) was added. The mixture was then heated with stirring for a fixed period. At the end of the reaction the product was cooled and dissolved in a minimum quantity of chloroform (e.g. 250 ml). This chloroform solution was washed with acidified water (e.g. 4 g 36% HCl in 100 ml water) and then three times with water alone (e.g. 100 ml). The washed chloroform solution of the polymer product was dried over anhydrous sodium sulphate and after filtration the solvent was removed by distillation at reduced pressure.

[0146] The polymer products obtained were analysed and characterised by:

[0147] Gel permeation chromatography (GPC): GPC was performed on a Shimadzu Prominence LC system equipped with an RI detector with a 300 mm×75 mm, 5 μm PLgel 100 Å and 300 mm×7.5 mm, 5 μm PLgel 500 Å column in series at 40° C. with a THF eluent at 1.0 ml/min. The method was calibrated with poly(styrene) standards with MW between 1000 and 10000.

[0148] Viscometry: Viscometry was performed on a TA Instruments Discovery Hybrid Rheometer using a 40 mm 2.008° cone plate geometry at 10 rad/s between −20 and 70° C.

[0149] Using this general method, a series of polymer products were produced. Details for each preparation and key properties of each product are outlined in the Table 1. Table 1 also contains data from a reference example: the commercial refrigeration lubricant Supercool PAG 46.

TABLE-US-00001 TABLE 1 Preparative examples Recipe Temper- Batch GPC Analysis Initiator TFPO ature Yield time M.sub.w/M.sub.n Viscometry, η (cP) at ° C. Example (g) (g) (° C.) (g) (hrs) M.sub.n M.sub.w (PDI) −10 0 20 40 60 1-F(A) EG 5.7 130.8 70 121.2 72 1078 1307 1.21 27122.2 7154.3 599.1 125.5 46.8 KOH 1.07 2-F(B) EG 5.34 135.8 50 118.6 72 1139 1379 1.22 28106.1 7341.6 627.7 132.4 49.3 KOH 1.0 3-F(C) EG 5.1 135.0 90 129.1 72 2069 2399 1.16 25726.3 6904.9 613.0 134.3 49.5 KOH 1.1 4-F(D) TFEA 1.1 135.8 70 127.9 48 1516 1712 1.13 16917.8 4267.3 444.0 109.4 44.5 KOH 1.1 5-F(F) TFEA 10 135 70 86.3 48 1478 1401 1.05 3066.9 824.9 130.2 40.1 18.1 KOH 2.0 Reference N/A N/A N/A N/A N/A 1141 1886 1.65 568.5 271.3 84.0 37.0 21.4 example: Supercool PAG 46 *EG = Ethylene glycol, TFEA = trifluoroethanol, TFPO = 3,3,3-trifluoro-2,3-epoxypropane

[0150] The results clearly show that by using the method of the invention polymers could be simply and easily produced with a significant improvement of molecular weight control (M.sub.W and M.sub.n) and polydispersity index (PDI) when compared to the reference example (Supercool PAG 46, a commercial PAG refrigeration lubricant). The properties of the product of example 5—F(F) were particularly good and the viscometry and GPC results for the Reference Example and Example 5—F(F) are shown in FIGS. 1-3.

[0151] Vapour-Liquid Equilibria (VLE)

[0152] Vapour-liquid equilibria data was measured in a static constant-volume apparatus consisting of a vessel of a precisely known internal volume, located in a temperature-controlled metal block. A magnetic stirring device was located inside the heated vessel. Heat transfer fluid, controlled at a constant temperature, was passed through the block to allow precise control of temperature inside the vessel. The cell was evacuated and then known amounts of each component were charged to the cell. The temperature of the cell was then varied stepwise from about −30° C. to +70° C. At each temperature, the cell temperature and pressure were logged continuously and recorded when stable conditions were reached.

[0153] The vapour-liquid equilibria data was measured for R-1234yf and the product of Example 5—F(F), as shown in FIG. 4. The system displays positive deviation from ideal behaviour and the raw experimental data shows that there is no region of liquid-liquid immiscibility over the temperature and composition range studied.

[0154] The vapour-liquid equilibria data was measured for R-1234yf and Supercool PAG 46, as shown in FIG. 5. The data shows that a region of liquid-liquid immiscibility may be present for mixtures at compositions 60% w/w R-1234yf and above. Below 50% w/w R-1234yf mixtures, no immiscibility is expected over the temperature range studied.

[0155] The results show that the product of Example 5—F(F) and R-1234yf are miscible in all proportions. The same miscibility cannot be seen with the commercial PAG refrigeration lubricant (Supercool PAG 46) and R-1234yf. Therefore, the product of Example 5—F(F) shows better properties than the commercial lubricant.

Example 6

Polymerisations Involving 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (HFIBO)

[0156] ##STR00009##

[0157] An initiator mixture was prepared by dissolving potassium hydroxide (85%, 0.27 g) in trifluoroethanol (1.25 g) with two drops of Aliquat 336 in a round bottomed flask. The mixture was stirred under cooling until all the KOH pellets had dissolved. Upon dissolution the flask was transferred to a hotplate, equipped with a condenser and 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (16.25 g) added via a dropping funnel. The hotplate was then heated to 70° C. and the mixture began refluxing 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 dissolve in tetrahydrofuran and was analysed by .sup.19F NMR spectroscopy which showed several very broad signals characteristic of polymers at −74.28, −75.08, −76.69 and −78.79 ppm (vs perfluorbenzene at −164.9 ppm). Evaporation of the solvent yielded a viscous white polymer.

Example 7

Polymerisations Involving 75% TFPO and 25% HFIBO

[0158] An initiator mixture was prepared by dissolving potassium hydroxide (85%, 0.26 g) in trifluoroethanol (1.25 g) with two drops of Aliquat 336 in a round bottomed flask. The mixture was stirred under cooling until all the KOH pellets had dissolved. Upon dissolution the flask was transferred to a hotplate and 3,3,3-trifluoro-2-(trifluoromethyl)-1,2-propenoxide (5.63 g) and TFPO (10.5 g) was added via a dropping funnel. The hotplate was then heated to 70° C. and the mixture began refluxing at 40° C. the flask was equipped with a chiller supplied condenser. After refluxing for 24 hours a polymer had formed, and the temperature of the reaction mixture was 65° C. After cooling the polymer was washed dissolution was attempted in chloroform, this layer was then washed and dissolved in tetrahydrofuran and analysed by .sup.19F NMR spectroscopy which showed several very broad signals characteristic of polymers at −73.61, −74.14, −75.89, −77.17 and −79.32 ppm (vs perfluorbenzene at −164.9 ppm). Evaporation of the solvent yielded a grey coloured polymer.

COMPARATIVE EXAMPLES

[0159] Comparative examples were carried out using a commercial PAG refrigeration lubricant (Supercool PAG 46) and the methods and product of Example 1 of WO 2017/098238.

[0160] The results clearly show a significant improvement in molecular weight control and polydispersity index when an initiator of ethylene glycol or trifluoroethanol and potassium hydroxide is used in the absence of solvent, see Table 2.

TABLE-US-00002 TABLE 2 Comparative examples Recipe GPC Analysis Temper- M.sub.w/M.sub.n Viscometry, η (cP) at ° C. Experiment Initiator (g) TFPO ature M.sub.n M.sub.w (PDI) −10 0 20 40 60 Reference N/A N/A N/A 1141 1886 1.65 568.5 271.3 84.0 37.0 21.4 example: Supercool PAG 46* Comparative t-BuOK 1.3 50 90 4063 5964 1.47 90100.4 21873.1 2153.7 435.7 158.4 Example 1: Example 1 WO2017/ 098238 Comparative EG 2.53 43.6 90 3722 4303 1.16 42921.1 14167.8 1274.1 269.97 102.9 Example 2: t-BuOK 5 Solvent free Comparative TFEA 1 49.4 110 1469 1815 1.24 10046.3 2460.2 248.6 60.3 24.4 Example 3: t-BuOK 1.16 Solvent free, change alcohol Comparative EG 1.0 50 89 947 1118 1.18 9354.2 2403.4 261.6 60.6 23.0 Example 4: KOH 1.11 Solvent free, change base *t-BuOK = potassium t-butoxide, EG = Ethylene glycol, TFEA = trifluoroethanol, TFPO = 3,3,3-trifluoro-2,3-epoxypropane

[0161] Developments of the Method of Preparation and Product of Example 5—F(F)

[0162] The procedure described above was used to prepare a series of variants of the product of example 5—F(F) by varying the composition of the initiator mix. Details for each individual preparation and results are presented in Table 3.

[0163] In these examples the number of repeating units in the polymer products, n, was estimated by GPC which showed that polymers could be made with n in the range of 6-34 or so.

[0164] Lubricating Properties of Polymers

[0165] The lubricating properties of the polymer products from the method and product development examples were determined using a TA Instruments Discovery Hybrid Rheometer by measuring the co-efficient of friction between a rotating ball bearing and three fixed ball bearings at 25° C. at different sliding speeds as a function of axial force, see Table 4.

[0166] The results confirm that the polymers of the invention are excellent lubricants on a par with Supercool PAG 46, which is a fully formulated commercial lubricant whose formulation includes additives designed to aid lubricity.

TABLE-US-00003 TABLE 3 Development of the method of preparation and product of Example 5-F(F) η at η at η at η at η at TFEA KOH TFPO Polymer n −10° C. −0° C. 20° C. 40° C. 60° C. Example (g) (g) (g) yield (g) M.sub.w M.sub.n PDI (GPC (cP) (cP) (cP) (cP) (cP) 5-F(F) 10 2 135 86.3 1478 1401 1.05 11 3066.9 824.9 130.2 40.1 18.1 5-F(F) 22.3 4.54 300 280 1706 1615 1.06 13 6548.0 1532.5 231.7 62.3 25.7 Scale up**  1a 5 1 65 39 1217 1154 1.05 9 829.2 263.5 53.0 18.4 8.8  2a 5 0.29 65 49.63 1403 1335 1.05 11 2491.9 683.5 113.0 35.2 15.7  3a 5 1 65.4 52.6 1463 1385 1.06 11 2731.7 740.3 119.6 36.8 16.3  4a 8.45 1 65 51.6 1036 995 1.04 7 335.8 121.9 29.2 11.0 5.4  5a 1.46 1 65 26.4 4032 3504 1.15 34 45437.0 12200.9 1113.8 235.2 87.1  6a 7.5 1.5 65 65 1280 1217 1.05 10 1391.4 414.3 76.1 25.1 11.8  7a 7.5 0.5 64.93 25.2 842 825 1.02 6 73.6 33.3 10.1 4.3 2.1  7b 7.5 0.5 64.93 25.2 929 902 1.03 6 187.9 75.9 20.5 8.3 4.2  8a 5 1 65.3 53.1 1486 1408 1.06 11 2749.2 740.0 113.8 34.7 15.2  9a 2.5 1.5 65.1 55.5 2756 2578 1.07 23 22562.1 5398.8 528.5 121.9 46.2 10a 5 1.71 64.9 57.71 1648 1554 1.06 13 4256.9 1050.4 149.2 43.1 18.9 11a 5 1 65 52.5 1419 1340 1.06 11 2390.8 629.0 102.1 31.8 14.1 12a 5 1 65 57.1 1530 1444 1.06 12 2939.4 786.9 129.9 38.0 16.4 13a 2.5 0.5 65 39.73 2024 1910 1.06 16 10415.6 2408.8 311.3 81.8 33.0 *TFEA = trifluoroethanol, TFPO = 3,3,3-trifluoro-2,3-epoxypropane **Because of the larger scale of this example the method was adapted. Thus, the initiator mix was prepared and heated to 70° C. and then the TFPO was added over 3-4 hours

TABLE-US-00004 TABLE 4 Lubricity of polymers from method and product development study Coefficient of Axial friction (μ) at Polymer force sliding speed (μm/sec): example (N) 20000 40000 60000 80000 Reference 5 0.097 0.096 0.095 0.094 example: 10 0.103 0.100 0.098 0.096 Supercool 15 0.105 0.101 0.098 0.096 PAG 46 20 0.107 0.102 0.100 0.098 25 0.108 0.104 0.102 0.100 30 0.110 0.107 0.104 0.103 35 0.112 0.109 0.107 0.105 40 0.113 0.111 0.109 0.107 5-F(F) 5 0.104 0.104 0.104 0.103 10 0.114 0.104 0.106 0.106 15 0.118 0.099 0.104 0.106 20 0.120 0.104 0.106 0.106 25 0.121 0.121 0.115 0.116 30 0.121 0.121 0.120 0.119 35 0.120 0.120 0.119 0.118 40 0.120 0.120 0.119 0.117 5-F(F) 5 0.101 0.099 0.097 0.097 Scale up 10 0.107 0.105 0.103 0.103 15 0.111 0.110 0.109 0.109 20 0.114 0.113 0.113 0.112 25 0.116 0.116 0.116 0.114 30 0.118 0.118 0.118 0.117 35 0.119 0.120 0.120 0.118 40 0.121 0.121 0.120 0.119

TABLE-US-00005 TABLE 4 continued: Lubricity of polymers from method and product development study Coefficient of friction (μ) Polymer Axial at sliding speed (μm/sec): example force (N) 20000 40000 60000 80000 1a 5 0.102 0.101 0.101 0.100 10 0.109 0.108 0.107 0.106 15 0.110 0.108 0.106 0.105 20 0.109 0.107 0.106 0.105 25 0.109 0.108 0.107 0.106 30 0.111 0.109 0.108 0.108 35 0.112 0.111 0.110 0.108 40 0.112 0.111 0.109 0.108 2a 5 0.104 0.103 0.102 0.101 10 0.109 0.108 0.106 0.105 15 0.110 0.108 0.107 0.106 20 0.111 0.109 0.108 0.107 25 0.112 0.111 0.110 0.109 30 0.113 0.112 0.111 0.111 35 0.114 0.114 0.113 0.112 40 0.115 0.115 0.115 0.114 3a 5 0.106 0.106 0.105 0.105 10 0.113 0.111 0.110 0.109 15 0.115 0.114 0.112 0.111 20 0.117 0.116 0.115 0.114 25 0.119 0.118 0.117 0.116 30 0.120 0.119 0.118 0.117 35 0.121 0.120 0.119 0.118 40 0.121 0.120 0.120 0.119

TABLE-US-00006 TABLE 4 continued: Lubricity of polymers from method and product development study Coefficient of friction (μ) Polymer Axial at sliding speed (μm/sec): example force (N) 20000 40000 60000 80000 4a 5 0.093 0.091 0.089 0.088 10 0.102 0.098 0.096 0.094 15 0.105 0.101 0.099 0.098 20 0.108 0.105 0.103 0.102 25 0.111 0.108 0.106 0.105 30 0.113 0.109 0.107 0.106 35 0.114 0.110 0.108 0.107 40 0.115 0.111 0.110 0.108 5a 5 0.102 0.098 0.096 0.096 10 0.111 0.114 0.118 0.118 15 0.121 0.124 0.127 0.125 20 0.129 0.130 0.130 0.129 25 0.132 0.134 0.133 0.132 30 0.134 0.136 0.135 0.134 35 0.136 0.138 0.137 0.136 40 0.137 0.139 0.138 0.136 6a 5 0.097 0.096 0.095 0.095 10 0.107 0.105 0.103 0.102 15 0.110 0.109 0.108 0.106 20 0.113 0.112 0.111 0.110 25 0.115 0.114 0.113 0.113 30 0.116 0.116 0.115 0.114 35 0.118 0.117 0.117 0.116 40 0.119 0.119 0.118 0.117

TABLE-US-00007 TABLE 4 continued: Lubricity of polymers from method and product development study Coefficient of friction (μ) Polymer Axial at sliding speed (μm/sec): example force (N) 20000 40000 60000 80000 7a 5 0.109 0.104 0.102 0.100 10 0.116 0.110 0.107 0.105 15 0.118 0.113 0.110 0.107 20 0.124 0.117 0.114 0.111 25 0.129 0.122 0.117 0.115 30 0.132 0.125 0.120 0.116 35 0.132 0.124 0.120 0.117 40 0.133 0.124 0.120 0.118 7b (7a 5 0.094 0.092 0.091 0.091 repeat) 10 0.101 0.085 0.086 0.085 15 0.104 0.102 0.101 0.100 20 0.107 0.104 0.103 0.102 25 0.109 0.107 0.105 0.104 30 0.111 0.109 0.107 0.107 35 0.113 0.110 0.109 0.108 40 0.114 0.110 0.109 0.108 8a 5 0.113 0.113 0.113 0.113 10 0.114 0.114 0.114 0.114 15 0.115 0.115 0.115 0.115 20 0.116 0.116 0.115 0.115 25 0.119 0.118 0.117 0.115 30 0.118 0.117 0.116 0.115 35 0.118 0.117 0.116 0.116 40 0.118 0.118 0.117 0.116

TABLE-US-00008 TABLE 4 continued: Lubricity of polymers from method and product development study Coefficient of friction (μ) Polymer Axial at sliding speed (μm/sec): example force (N) 20000 40000 60000 80000  9a 5 0.113 0.115 0.116 0.116 10 0.123 0.125 0.125 0.126 15 0.127 0.129 0.129 0.129 20 0.130 0.131 0.131 0.130 25 0.133 0.134 0.133 0.131 30 0.134 0.136 0.135 0.133 35 0.136 0.137 0.136 0.134 40 0.137 0.138 0.137 0.135 10a 5 0.103 0.104 0.104 0.103 10 0.110 0.111 0.111 0.111 15 0.113 0.113 0.113 0.112 20 0.115 0.115 0.114 0.113 25 0.114 0.112 0.112 0.113 30 0.117 0.118 0.117 0.116 35 0.119 0.119 0.118 0.117 40 0.119 0.119 0.118 0.118 11a 5 0.113 0.112 0.112 0.112 10 0.114 0.114 0.113 0.113 15 0.115 0.114 0.114 0.113 20 0.115 0.115 0.114 0.113 25 0.116 0.116 0.115 0.114 30 0.117 0.117 0.116 0.115 35 0.118 0.117 0.117 0.116 40 0.118 0.118 0.117 0.116

TABLE-US-00009 TABLE 4 continued: Lubricity of polymers from method and product development study Coefficient of friction (μ) Polymer Axial at sliding speed (μm/sec): example force (N) 20000 40000 60000 80000 12a 5 0.101 0.102 0.102 0.102 10 0.109 0.109 0.109 0.108 15 0.112 0.112 0.111 0.110 20 0.115 0.114 0.113 0.113 25 0.116 0.116 0.115 0.114 30 0.117 0.117 0.116 0.115 35 0.118 0.117 0.117 0.116 40 0.118 0.118 0.117 0.116 13a 5 0.117 0.119 0.120 0.120 10 0.120 0.121 0.121 0.121 15 0.122 0.122 0.122 0.121 20 0.124 0.123 0.123 0.123 25 0.125 0.125 0.125 0.124 30 0.125 0.126 0.126 0.125 35 0.126 0.126 0.126 0.126 40 0.126 0.127 0.127 0.126