HIGH DENSITY POLYESTER PRODUCT, COMPOSITION AND USE

Abstract

The present invention relates to a polyester product having a relatively high atypical density of greater than 1 g/cm.sup.3 at 25° C., the polyester product comprises the reaction product of one or more C2 to C12 polybasic acid and one or more polyol. The invention also relates to methods of making the polyester product, compositions containing or comprising the polyester product and the use of such compositions. More especially, the polyester containing compositions may advantageously be utilised in aqueous environment applications, or other applications, where environmental containment is an important consideration.

Claims

1. A polyester product comprising the reaction product of: a) one or more C2 to C12 polybasic acid, and b) one or more polyols, wherein the polyester product has a density of greater than 1 g/cm.sup.3 at 25° C.

2. The polyester product of claim 1, having a density of greater than 1.03 g/cm.sup.3 at 25° C.

3. The polyester product of claim 2, having a density of greater than 1.05 g/cm.sup.3 at 25° C.

4. The polyester product of claim 1, having a density of greater than 1 g/cm.sup.3 at 4° C.

5. The polyester product of claim 4, having a density of greater than 1.04 g/cm.sup.3 at 4° C.

6. The polyester product of claim 4, having a density of greater than 1.06 g/cm.sup.3 at 4° C.

7. The polyester product of claim 1, having a kinematic viscosity at 40° C. of up to 10000 mm.sup.2/s.

8. The polyester product of claim 7, having a kinematic viscosity at 40° C. of between 3 and 2500 mm.sup.2/s.

9. The polyester product of claim 8, having a kinematic viscosity at 40° C. of between 4 and 1000 mm.sup.2/s.

10. The polyester product of claim 1, having a kinematic viscosity at 4° C. of no greater than 100000 mm.sup.2/s.

11. The polyester product of claim 10, having a kinematic viscosity at 4° C. of between 200 and 1000 mm.sup.2/s.

12. The polyester product of claim 1, further comprising c) an end-cap.

13. The polyester product of claim 12, wherein c) the end cap is selected from one or more of the following: mono-basic acids, mono-alcohols, and epoxides.

14. The polyester product of claim 13, wherein c) the end cap, selected includes a mono-basic acid or a mono-alcohol.

15. The polyester product of claim 14, wherein c) the end cap selected is a mono-alcohol and is a glycol ether.

16. The polyester product of claim 1, wherein the molecular ratio of a):b):c) in the polyester product is in the range 0.1 to 1:0.1 to 1:0 to 1.

17. The polyester product of claim 16, wherein the molecular ratio of a):b):c) in the polyester product is in the range 0.1 to 0.8:0.1 to 0.5:0.1 to 0.2.

18. The polyester product of claim 1, wherein a) the one or more C2 to C12 polybasic acid of the polyester product may be selected from oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, citric acid, trimellitic acid, suberic acid, 2,5-furandicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, butane tetracarboxylic acid, azelaic acid, sebacic acid, dodecanedioic acid, heptane dicarboxylic acid, octenylsuccinic acid, itaconic acid, 2,6 naphthalene dicarboxylic acid, esters thereof, and anhydrides thereof.

19. The polyester product of claim 1, wherein a) the one or more C2 to C12 polybasic acid comprises one or more diacid or triacid.

20. The polyester product of claim 1, wherein a) the one or more C2 to C12 polybasic acid is a C4 to C8 polybasic acid.

21. The polyester product of claim 1, wherein b) the one or more polyols of the polyester product is a diol, triol or hexol.

22. The polyester product of claim 1, wherein b) the one or more polyol of the polyester product is a C2 to C12 polyol.

23. The polyester product of claim 1, wherein b) the one or more polyol of the polyester product is a C2 to C10 polyol.

24. The polyester product of claim 1, wherein b) the one or more polyol of the polyester product is selected from propolyene glycol, butanediol (butylene glycol), tri-propylene glycol, di-propolyene glycol, glycerol, trimethylopropane, sorbitol, other sugar alcohols, and alkoxylates thereof, or a glycerol.

25. The polyester product of claim 1, wherein b) the one or more polyol is a glycol.

26. The polyester product of claim 1, wherein b) the one or more polyol consists of two polyols independently selected.

27. The polyester product of claim 1, having a hydroxyl value below 100 mgKOH/g.

28. The polyester product of claim 1, having a saponification (SAP) value of between 300 and 410.

29. The polyester product of claim 1, wherein the polyester product has a seawater biodegradability of greater than 60%, achieved during the 28 day test period as measured in accordance with the Organisation for Economic Cooperation and Development standard test OECD 306.

30. The polyester product of claim 1, wherein the polyester product provides a positive ecotoxicology profile when tested in one or more of the following standard tests: OSPAR Commission 2006 Part B. Protocol for a fish acute toxicity test, ISO 10253 (2016) Water quality—Marine algal growth inhibition test with Skeletonema sp, ISO 14669 (1999) Water Quality—Determination of acute lethal toxicity to marine copepods (Copepoda; Crustacea), and, OSPAR Commission (2006) Part A. (-A sediment bioassay using an amphipod Corophium sp).

31. The polyester product of claim 1, wherein the polyester product is not soluble in water.

32. A method of making a polyester product as defined in claim 1, the method comprising reacting said a) one or more C2 to C12 polybasic acid and said b) one or more polyol, and optionally c) an end cap.

33. The method of claim 32, wherein the reaction is a transesterification reaction, where condensation between a) the polybasic acid and b) the one or more polyol provides formation of an ester linkage between the two reactants.

34. The method of claim 32, wherein the reaction is catalysed, and the reactants a) and b) are brought in to contact with a suitable catalyst.

35. The method of claim 32, wherein the reaction if performed at a reaction temperature of between 100° C. and 250° C.

36. The method of claim 32, wherein the reaction if performed under a reduced pressure.

37. The method of claim 32, further comprising the step of intermittently sampling the materials present in the reaction vessel and assessing their physical properties.

38. The method of claim 32, further comprising one or more of the following optional steps: treatment with an absorbate, introduction of a filter aid and subsequent filtration, and/or introduction of a bleaching medium.

39. A composition comprising a polyester product as defined in claim 1.

40. The composition of claim 39, comprising between 0.1 weight % and 99 weight % polyester product based on the total composition by weight.

41. The composition of claim 39, wherein the composition comprises at least 70 weight % polyester product based on the total composition by weight.

42. The composition of claim 39, further comprising one or more of the following additional materials: an additional lubricant, a corrosion inhibitor, an anti-wear additive, an extreme pressure additive, an antioxidant, and a biocide.

43. The composition of claim 42, wherein the one or more additional materials are present in an amount from between 0.01 weight % and 20 weight % of the total composition by weight.

44. The composition of claim 39, wherein the composition is a lubricant which can be considered as an environmentally acceptable lubricant.

45. The composition of claim 39, wherein the composition is a subsea control fluid.

46. The composition of claim 39, wherein the composition is a hydraulic fluid, and preferably a sub-sea actuator fluid.

47.-48. (canceled)

Description

EXAMPLES

[0094] The present invention will now be described further by way of example only with reference to the following Examples.

[0095] All parts and percentages are given by weight unless otherwise stated.

[0096] It will be understood that all tests and physical properties listed have been determined at atmospheric pressure and room temperature (i.e. about 20° C.), unless otherwise stated herein, or unless otherwise stated in the referenced test methods and procedures

Example 1—Polyester Product of Dimethyl Adipate and Neopentyl Glycol End Capped with Tri(Propylene Glycol) Methyl Ether

[0097] At ambient pressure and temperature 216.82 g (1.24 moles) of dimethyl adipate, 77.78 g (0.75 moles) of neopentyl glycol and 205.40 g (1.00 moles) of tri(propylene glycol) methyl ether were charged into a 1 litre five-necked flask reaction vessel fitted with a mechanical stirrer, a thermometer and a nitrogen inlet. 0.1 g of tetra-n-butyl titanate catalyst was subsequently added. The reactants were gradually heated from ambient temperature up to 180° C. and held at this temperature while the reactants and catalyst were agitated via stirring under a nitrogen atmosphere for between 1 and 2 hours. The reactant mixture was then gradually heated up to a reaction temperature of 240° C., over a period of 2 to 4 hours. The temperature of reaction was then held at 240° C. for 2 to 3 hours until a point where little or no further distillate could be seen coming off the reaction. The pressure inside the reaction vessel was then reduced form atmospheric pressure to 200 mbar over a time period of between 4 to 6 hours; this reduction in pressure was used to force the reaction towards completion in a time efficient manner. The elevated temperature and reduced pressure was maintained until the reaction product reached a desired viscosity, before cooling to room temperature and discharging the polyester product thereby formed.

[0098] The resulting polyester product was a liquid at room temperature with a kinematic viscosity at 40° C. of 48 mm.sup.2/s, and a density at 25° C. of 1.06 g/cm.sup.3.

Example 2—Polyester Product of Dimethyl Adipate and Di(Propyl Glycol) End Capped with Di(Propyl Glycol) Mono Methyl Ether

[0099] At ambient pressure and temperature 350.02 g, (2 moles) of dimethyl adipate, 161.75 g (1.2 moles) of di(propyl glycol) and 238.22 g (1.6 moles) of di(propyl glycol) mono methyl ether were charged into a 1 litre five-necked flask reaction vessel fitted with a mechanical stirrer, a thermometer and a nitrogen inlet. A nitrogen purge was performed along with agitation of the reactants via stirring. The reaction vessel temperature was then raised to 180° C. Once the temperature of 180° C. was reached 0.1 g of tetra-n-butyl titanate catalyst was added. The temperature was then increased to the temperature of reaction at 220° C. and this temperature was maintained. The pressure within the reaction vessel was then slowly reduced from atmospheric to 200 mbar to aid completion of the reaction. These conditions were maintained until the reaction product reached a desired viscosity, before cooling to room temperature and discharging the polyester product thereby formed.

[0100] The resulting polyester product was a liquid at room temperature with a kinematic viscosity at 40° C. of 55 mm.sup.2/s and a density at 20° C. of 1.06 g/cm.sup.3. The kinematic viscosity at 4° C. was 431 mm.sup.2/s and at 4° C. the product had a density of 1.08 g/cm.sup.3.

Example 3—Polyester Product of Adipic Acid and Di(Propylene Glycol), No End Cap

[0101] At ambient pressure and temperature 1169.10 g (8.7 moles) of di(propylene glycol) and 841.33 g (5.8 moles) of adipic acid were charged into a five-necked flask reaction vessel fitted with a mechanical stirrer, a thermometer and a nitrogen inlet. 1.00 g of tetra-n-butyl titanate catalyst was subsequently added. A nitrogen purge was performed along with agitation of the reactants via stirring. The reaction vessel was then heated up to the reaction temperature 220° C. with continued stirring under a nitrogen atmosphere. The progress of the reaction was monitored by measuring the reaction product acid value. The reaction was stopped once the acid value obtained was <0.1 mg KOH/g.

[0102] The resulting polyester product was a viscous liquid, with a hydroxyl value of 180 mgKOH/g, saponification value of 361 mgKOH/g and an acid value of 0.09 mgKOH/g. The kinematic viscosity at 40° C. was 270 mm.sup.2/s and had a density of 1.09 g/cm.sup.3. The kinematic viscosity at 4° C. was 6769 mm.sup.2/s and at 4° C. the product had a density of 1.11 g/cm.sup.3.

Example 4—Formulation and Application Testing

[0103] The polyester product prepared from Example 2 above was then tested for application as a lubricant; as described above its relatively high density renders it suitable for use in marine, and particularly subsea applications, but given the difficulty of running in situ testing for such applications a simple anti-wear test (described below) was utilised to assess the products utility for such applications where a degree of lubricancy is desirable. In addition, the polyester product was blended with other optional materials to further improve the properties of the polyester product as a lubricant.

[0104] The formulations prepared and the anti-wear test results are provided below.

[0105] Anti-Wear Test Method

[0106] The anti-wear tests were carried out in accordance with ASTM D4172 Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method) (40 kg applied load, speed 1200 rpm, time 1 hour).

[0107] The average wear scar diameter (WSD) in millimetres (mm) was recorded and is provided in Table 1 below for each of the formulations including Example 2 polyester product tested.

[0108] Additional Materials

[0109] Irgalube™ 349 ex. BASF—a mixture of amine phosphates.

[0110] Priolube™ 1415 ex. Croda—a mono-ester.

[0111] Priolube™ 1973 ex. Croda—an ester.

[0112] Span™ 80 ex. Croda—sorbitane mono-oleate.

[0113] Span™ 85 ex. Croda—sorbitan trioleate.

[0114] Polartech™ MA3408T ex. Italmatch Chemicals—tall oil diethanolamide.

[0115] Trilauryl Phosphite.

[0116] Ucon™ OSP-46 ex. Dow Performance Lubricants—an oil-soluble polyalkylene glycol (PAG).

[0117] Example Formulation Details and WSD Data

TABLE-US-00001 TABLE 1 (note that Example 2 polyester product was employed to provide the total 100 weight % in each formulation). Formulation Weight Weight Weight WSD Material % Material % Material % (mm) (Example 2 1.080 Polyester Product) Irgalube 0.5 0.487 349 Priolube 1 0.940 1973 Tall oil 0.5 0.907 diethanolamide Trilauryl 2 0.940 Phosphite Priolube 20 Irgalube 0.1 1.073 1415 349 Ucon OSP-46 10 Span 85 5 0.880 Ucon OSP-46 20 Span 85 2 0.900 Ucon OSP-46 15 Span 85 1 0.967 Ucon OSP-46 15 Span 85 2 0.867 Ucon OSP-46 10 Span 85 2 0.880 Ucon OSP-46 10 Span 85 2 Span 80 1 0.947 Ucon OSP-46 10 Span 85 2 Span 80 2 0.967

[0118] The WSD achieved by the polyester product of Example 2 indicates that it provides sufficient lubricancy to be useful in some applications, and in particular as an actuator fluid.

[0119] It can be clearly seen from the data above that the inclusion of additional materials at low addition rates allows for provision of a formulation with enhanced lubricancy, which may be desirable for some applications. However, it can also be seen that the addition rates of the additional materials can be increased beyond an optimal addition rate, at which point the WSD improvements are lost. The additional materials exemplified herein were chosen to show that the polyester product of Example 2 has compatibility with a wide range of existing materials which may be incorporated into lubricant formulations for many uses; they are not untended to be limiting upon the scope of the present invention.