Use of at least one mono- or polyhydroxybenzene or derivative as antioxidant in linear olefins

Abstract

Use of antioxidants during storage and / or transport of linear olefins, in particular alpha-olefins.

Description

Technical Field

[0001] This invention relates to inhibiting the oxidation of straight-chain olefins, particularly α-olefins, during storage and / or transportation. Background Technology

[0002] Linear-chain olefins are hydrocarbons having 6 to 24 carbon atoms and containing at least one double bond. Within linear-chain olefins, a specific subgroup called α-olefins can be identified. These α-olefins have at least one double bond at the first position, namely a terminal carbon-carbon double bond. Linear-chain olefins can react with air or oxygen to form undesirable peroxides and other oxidation products. These undesirable peroxides and oxidation products can cause odor formation and / or discoloration. These undesirable products can also affect the performance of catalysts used to prepare polyalphaolefins.

[0003] Solutions have been proposed to mitigate this phenomenon; in particular, BHT (butylated hydroxytoluene) is used for the storage and transport of α-olefins to avoid undesirable reactions. However, BHT is often accused of being an endocrine disruptor and has toxic effects on the liver, kidneys, and lungs when ingested in very large doses. BHT is also suspected of having the potential for bioaccumulation in aquatic species.

[0004] The specific object of this invention is to provide a safer alternative to BHT that has at least equivalent or improved effectiveness in the preservation of straight-chain olefins. Summary of the Invention

[0005] According to one aspect, the present invention relates to the use of at least one mono- or polyhydroxybenzene or its derivatives for inhibiting the oxidation of linear olefins, particularly during storage and / or transportation.

[0006] According to another aspect, the present invention relates to the use of at least one mono- or poly-hydroxybenzene or its derivatives as a substitute for BHT.

[0007] According to a third aspect, the present invention relates to a composition comprising:

[0008] (i) α-olefins, selected from the group consisting of 1-octene, 1-hexene, or 1-decene, and

[0009] (ii) At least one mono- or poly-hydroxybenzene or a derivative thereof. Attached Figure Description

[0010] Figure 1 and Figure 2 Photographs of samples from Examples 1 to 13 after 90 days of storage. Detailed Implementation

[0011] In a first aspect, the present invention relates to the use of at least one mono- or polyhydroxybenzene or its derivatives for inhibiting the oxidation of linear olefins, particularly during storage and / or transportation.

[0012] In this disclosure, the term "oxidation inhibition" refers to the ability of a compound to prevent oxidation, degradation, and discoloration of a valuable product. Therefore, oxidation inhibition is crucial for improving the stability of valuable products during storage or transport. Typically, when nitrogen covering is not feasible, compounds suitable for oxidation inhibition are added to the valuable product.

[0013] Throughout this disclosure, the term "straight-chain olefin" refers to a compound having a straight chain of carbon atoms, preferably containing 6 to 24 carbon atoms and containing at least one carbon-carbon double bond.

[0014] Among straight-chain alkenes, a specific group of straight-chain alkenes can be named straight-chain α-olefins. Throughout this disclosure, the term "straight-chain α-olefin" refers to a compound having a straight chain of carbon atoms, preferably comprising 6 to 24 carbon atoms, and containing a carbon-carbon double bond between the first and second carbon atoms in the straight chain. Straight-chain α-olefins can also be referred to as terminal olefins or terminal alkenes. Straight-chain α-olefins can, for example, refer to 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

[0015] Throughout this disclosure, the term "effective amount" refers to the minimum amount of at least one mono- or poly-hydroxybenzene or a derivative thereof that has been observed to improve the inhibition of linear olefin oxidation.

[0016] According to the present invention, the straight-chain olefin can be a straight-chain olefin having 6 to 24 carbon atoms. Preferably, the straight-chain olefin can be an α-olefin, and more preferably selected from the group consisting of 1-octene, 1-hexene or 1-decene.

[0017] According to the present invention, the at least one mono- or poly-hydroxybenzene or its derivative can be used as a substitute for BHT. Advantageously, mono- or poly-hydroxybenzene or its derivative provides superior performance equivalent to BHT, while being safer from a toxicological point of view.

[0018] According to the present invention, the at least one mono- or poly-hydroxybenzene or its derivative may be a compound having formula (I):

[0019]

[0020] Each R1 is independently selected from the following groups:

[0021] - Hydroxyl group,

[0022] -C1-C6 straight-chain or branched alkyl groups,

[0023] -C1-C6 straight-chain or branched olefins,

[0024] -OR2, wherein R2 is selected from the group consisting of: C1-C6 straight-chain or branched alkyl, C1-C6 straight-chain or branched olefin, and n = 1, 2, 3, 4 or 5, preferably 1 or 2.

[0025] Preferably, when one of R1 is a hydroxyl group, the compound having formula (I) contains two hydroxyl groups, preferably in the ortho position.

[0026] Preferably, the at least one mono- or polyhydroxybenzene or its derivative may be selected from the group consisting of catechol, tert-butylcatechol and eugenol.

[0027] Advantageously, the use of at least one mono- or poly-hydroxybenzene or its derivative can avoid the formation of color and / or odor in straight-chain olefins.

[0028] According to the present invention, an effective amount of at least one mono- or polyhydroxybenzene or its derivative can be used to inhibit the oxidation of linear olefins, particularly during storage and / or transportation. Typically, the amount of the at least one mono- or polyhydroxybenzene or its derivative can be higher than 10 ppm, preferably higher than 15 ppm, and even more preferably higher than 20 ppm. Typically, the amount of the at least one mono- or polyhydroxybenzene or its derivative can be lower than 500 ppm, preferably lower than 450 ppm, and even more preferably lower than 400 ppm. In this case, more than one mono- or polyhydroxybenzene or its derivative can be used, where these amounts refer to the total amount of the mono- or polyhydroxybenzene or its derivative used to inhibit oxidation.

[0029] In practice, the total amount of at least one mono- or poly-hydroxybenzene or its derivative depends on the straight-chain olefin used in this invention. Various parameters can affect the amount of mono- or poly-hydroxybenzene or its derivative, such as temperature, humidity, etc.

[0030] According to another embodiment, the present invention relates to a composition comprising:

[0031] (i) α-olefins, selected from the group consisting of 1-octene, 1-hexene, or 1-decene, and

[0032] (ii) At least one mono- or poly-hydroxybenzene or a derivative thereof.

[0033] Preferably, at least one mono- or polyhydroxybenzene or its derivative in the composition of the present invention can be used as a substitute for BHT.

[0034] Preferably, at least one mono- or poly-hydroxybenzene or its derivative used in the composition can be a compound having formula (I):

[0035]

[0036] Each R1 is independently selected from the following groups:

[0037] -hydroxyl group,

[0038] -C1-C6 straight-chain or branched alkyl groups,

[0039] -C1-C6 straight-chain or branched olefins,

[0040] -OR2, wherein R2 is selected from the group consisting of: C1-C6 straight-chain or branched alkyl, C1-C6 straight-chain or branched olefin, and n = 1, 2, 3, 4 or 5, preferably 1 or 2.

[0041] Preferably, when one of R1 is a hydroxyl group, the compound having formula (I) contains two hydroxyl groups, preferably in the ortho position.

[0042] Preferably, the at least one mono- or polyhydroxybenzene or its derivative may be selected from the group consisting of catechol, tert-butylcatechol and eugenol.

[0043] Advantageously, an effective amount of at least one mono- or polyhydroxybenzene or its derivative can be used in the compositions of the present invention to inhibit the oxidation of linear olefins, particularly during storage and / or transportation. Typically, the amount of the at least one mono- or polyhydroxybenzene or its derivative can be higher than 10 ppm, preferably higher than 15 ppm, and even more preferably higher than 20 ppm. Typically, the amount of the at least one mono- or polyhydroxybenzene or its derivative can be lower than 500 ppm, preferably lower than 450 ppm, and even more preferably lower than 400 ppm. In this case, more than one mono- or polyhydroxybenzene or its derivative can be used, where these amounts refer to the total amount of the mono- or polyhydroxybenzene or its derivative used to inhibit oxidation.

[0044] In practice, the total amount of at least one mono- or poly-hydroxybenzene or its derivative depends on the straight-chain olefin used in this invention. Various parameters can affect the amount of mono- or poly-hydroxybenzene or its derivative, such as temperature, humidity, etc.

[0045] Advantageously, the compositions of the present invention exhibit superior performance equivalent to compositions containing BHT, while being safer from a toxicological point of view.

[0046] The following examples illustrate the present invention, but do not limit its scope.

[0047] Examples 1 to 13 – Preparation of compositions in 1-octene

[0048]

[0049] TBC refers to tert-butylcatechol, PC refers to catechol, and EUG refers to eugenol.

[0050] The effectiveness of Examples 1 to 9 (of the present invention) in inhibiting oxidation was verified by the following tests. Samples 1 to 13 were placed in a water bath at 30°C and kept for 90 days.

[0051] Antioxidant performance measured by GC

[0052] Antioxidant performance was analyzed by GC at 21, 56 and 90 days, and 1-octene content at 21, 56 and 90 days was evaluated compared with 1-octene content at the start of the test.

[0053] 1-Octenene content = (peak area after "n" days) / (peak area at the start of the test) 100

[0054]

[0055] In addition, visually assess whether the use of PC, EUG, or TBC affects the 1-octene sample. Analyze after 21, 56, and 90 days of storage.

[0056] This test shows that using PC, EUG, or TBC (Examples 1 to 9) has no effect on the color of 1-octene. In fact, the samples are not significantly different from the control samples (Examples 12 to 13). See also Figure 1 and Figure 2 It is a photo of the sample after 90 days of storage.

[0057] These results indicate that BHT can effectively replace mono- or polyphenols or their derivatives, particularly catechol, tert-butylcatechol, or eugenol, to inhibit the oxidation of straight-chain olefins, especially straight-chain α-olefins.

[0058] Examples 14 to 18 – Preparation of compositions in 1-decene

[0059]

[0060] TBC refers to tert-butylcatechol, PC refers to catechol, and EUG refers to eugenol.

[0061] The effectiveness of Examples 14 to 16 (of the present invention) in inhibiting oxidation was verified by the following tests. Samples 14 to 18 were placed in an oven at 30°C and aged for 120 days, and it was found that due to the inherent stability of 1-decene at 30°C, there was no significant degradation of 1-decene in all five samples. To demonstrate the effectiveness of the various antioxidants, the samples were subsequently placed in an oil bath at 60°C and aged for another 90 days.

[0062] Antioxidant performance measured by GC

[0063] The antioxidant properties of the samples were analyzed by GC at 60°C after 14, 28, 56, and 90 days, based on the 1-decene content. The results of the 90-day accelerated assay showed that TBC, PC, EUG, and BHT all exhibited good antioxidant properties, with PC and TBC showing slightly better antioxidant properties than BHT and EUG.

[0064] 1-Decanene content = (peak area after "n" days) / (peak area at the start of the test) 100

[0065]

[0066] Furthermore, all samples remained clear in color after being stored at 60°C for 90 days, indicating that the antioxidant product had no adverse effect on the color of 1-decene.

Claims

1. Use of at least one mono- or polyhydroxybenzene or its derivative for inhibiting the oxidation of linear olefins, particularly during storage and / or transport.

2. The use according to claim 1, wherein, The straight-chain olefin is a straight-chain olefin having 6 to 24 carbon atoms.

3. The use according to claim 1 or 2, wherein, The straight-chain olefin is an α-olefin, preferably 1-octene, 1-hexene, or 1-decene.

4. The use according to any one of claims 1 to 3, wherein, At least one mono- or poly-hydroxybenzene or its derivative is used as a substitute for BHT.

5. The use according to any one of claims 1 to 4, wherein, The at least one mono- or poly-hydroxybenzene or its derivative is a compound having formula (I): Each R1 is independently selected from the following groups: -hydroxyl group, -C1-C6 straight-chain or branched alkyl groups, -C1-C6 straight-chain or branched olefins, -OR2, wherein R2 is selected from the group consisting of: C1-C6 straight-chain or branched alkyl, C1-C6 straight-chain or branched olefin, and n = 1, 2, 3, 4 or 5, preferably 1 or 2.

6. The use according to any one of claims 1 to 5, wherein, The at least one mono- or poly-hydroxybenzene or its derivative is selected from the group consisting of catechol, tert-butylcatechol and eugenol.

7. Use according to any one of claims 1 to 6 for avoiding the formation of color and / or odor in straight-chain olefins.

8. The use according to any one of claims 1 to 7, wherein, The effective amount of at least one mono- or polyhydroxybenzene or its derivative is used to inhibit the oxidation of linear olefins, particularly during storage and / or transportation, and the effective amount is preferably from 10 ppm to 500 ppm.

9. A composition comprising: (i) α-olefins, selected from the group consisting of 1-octene, 1-hexene, or 1-decene, and (ii) At least one mono- or poly-hydroxybenzene or a derivative thereof.

10. The composition according to claim 9, wherein, At least one mono- or poly-hydroxybenzene or its derivative is used as a substitute for BHT.

11. The composition according to any one of claims 9 to 10, wherein, The at least one mono- or poly-hydroxybenzene or its derivative is a compound having formula (I).

12. The composition according to any one of claims 9 to 11, wherein, The at least one mono- or poly-hydroxybenzene or its derivative is selected from the group consisting of catechol, tert-butylcatechol and eugenol.

13. The composition according to any one of claims 9 to 12, wherein, The effective amount of at least one mono- or polyhydroxybenzene or its derivative is used to inhibit the oxidation of linear olefins, particularly during storage and / or transportation, and the effective amount is preferably from 10 ppm to 500 ppm.

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