Natural 1,2-alkanediol, composition containing natural 1,2-alkanediol and preparation process thereof

Abstract

Incorporated herein is a process for synthesizing bio-1,2-alkanediols, comprising: providing a bio-olefin having a carbon chain of about 5 to about 20 carbon atoms and at least about 80%, at least about 92%, and / or at least about 95% bio-1-olefin regioselectivity; and converting the bio-olefin to a bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms. Also included herein is a method for treating a catalyst that can be incorporated into a process for synthesizing bio-1,2-alkanediols. Such bio-1,2-alkanediols are used alone as antimicrobial materials in compositions and products, or used in conjunction with existing biocompounds and / or antimicrobial agents, preservatives, alternative preservative systems, and / or barrier technology components. Bio-1,2-alkanediols are incorporated into natural and bio-based pathways to produce antimicrobial effects in various compositions, such as cosmetics, pharmaceutical products, industrial and household products.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This U.S. nonprovisional patent application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 62 / 623,985, filed on January 30, 2018, entitled “NATURAL 1,2-ALKANEDIOLS, COMPOSITIONS HAVING NATURAL 1,2-ALKANEDIOLS, AND METHODS OF MAKING THE SAME,” the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The invention herein relates to the field of natural and renewable (i.e., sustainable) antimicrobial components that can be used as alternative preservative systems in compositions suitable for a variety of industries, including personal care, household and institutional or industrial cleaning products, medical or other related uses, and especially in human care compositions. The invention more specifically relates to the preparation of natural and renewable 1,2-alkanediols, methods for preparing natural and renewable 1,2-alkanediols, and compositions comprising such 1,2-alkanediols prepared from natural and renewable ("sustainable") raw materials. Background Art

[0004] In most countries, including the United States, cosmetics and / or personal care ("personal care products") and other consumer products are manufactured and packaged under clean but usually not sterile conditions, and many are sold in non-sterile form. As a result, the products may be contaminated with small amounts of (usually harmless) bacteria, molds, or yeast spores (collectively referred to as "microorganisms"). In addition, once a consumer purchases, opens, and begins to use such a product, further contamination may occur. For example, in personal care products, small amounts of microorganisms from the air or the consumer's skin may further contaminate the product.

[0005] Over time, during shipping, storage or use, a negligible initial microbial population can increase to significant levels sufficient to cause product discoloration or contamination, including the appearance of visible mold, which can affect the usability or performance of the product. In the case of personal care products or other consumer products (e.g., vitamins, etc.) that are applied or ingested, it can also have health effects and in some cases can cause adverse skin reactions (including infections) when applied.

[0006] To address the problem of microbial growth, manufacturers in the personal care industry and other industries typically add chemical preservatives, which are often petrochemical in nature, to such products and compositions. However, the type and amount of preservatives that can be used are limited in several ways: (1) legislative aspects (in some countries, the use of specific preservatives is prohibited); (2) technical aspects (the type / amount of preservative must demonstrate its efficacy by meeting certain empirically evaluated criteria ("challenge experiments"); (3) consumer preference aspects (consumers may consider certain preservative chemicals to be undesirable, such as petroleum-based or unsustainable products, and therefore products including them are not commercially viable); (4) logistical aspects (e.g., the preservative selected must be effective in a relevant chemical environment (where parameters such as pH, hydrophobicity / hydrophilicity, etc. can vary) and be cost-effective); and (5) sustainability aspects, i.e., it should be prepared using sustainable processes and raw material sources as further described herein.

[0007] It is also desirable to develop alternatives to traditional preservation and to find more user-friendly chemical ingredient combinations obtained from sustainable and renewable resources (i.e., "raw materials"). These natural and renewable antimicrobial components and alternatives to traditional preservatives ("alternative preservations") should provide consumers with equal or better protection and performance.

[0008] In order to solve the problems of traditional preservatives, the applicant has developed a prior art preservative for personal care compositions, which does not include parabens, formaldehyde donors or chlorinated compounds, which can be used for all types of personal care formulations (e.g., "leave-on" and "rinse-off" products). Such paraben-free or other non-petroleum-based alternative preservative products are attractive to consumers. Paraben-free preservatives show efficacy against a wide spectrum of microorganisms under various pH conditions, particularly around neutral pH conditions (which are usually in or on the human body). The preservative is described in U.S. Patent Publication No. 2017 / 0360035 A1, wherein one component in the preservative system is 1,2-alkanediol.

[0009] Another attempt in the art to reduce the use of traditional preservatives is to apply "hurdle technology". Hurdle technology is the practice of applying several types of confinement or preservation materials or processes so that microorganisms have a "hurdle" to overcome before they can proliferate to spoilage levels (e.g., adding some pH-altering substances to reduce proliferation and adding small amounts of preservatives or other compounds that together hinder or form a "hurdle" to microbial growth). The use of alternative preservations can be steps or "hurdles" in hurdle technology.

[0010] There is a need in the art for further development of "alternative preservative" additives. These alternative preservative systems include consumer-friendly, paraben-free materials that move away from traditional preservatives or antimicrobials and toward "natural" and "sustainable" ("renewable") formulations and raw materials, as those terms are defined below.

[0011] Applicants believe that one diol used for preservation (caprylyl glycol) is the fastest growing alternative preservative component in the world. Other 1,2-alkanediols such as 1,2-hexanediol, 1,2-decanediol and 1,2-dodecanediol are also becoming more popular and play a role in alternative preservative formulations.

[0012] An example of a reaction sequence for the preparation of octanediol (1,2-octanediol) using olefins as the key starting material is shown below. The starting material used is petrochemically derived 1-octene:

[0013]

[0014] In the above reaction sequence, petrochemically derived 1-octene is reacted in the presence of formic acid and peroxide to form an intermediate chemical mixture, which undergoes a further ring-opening reaction with sodium hydroxide, for example in water, to complete the preparation of 1,2-octanediol. This provides an excellent alternative preservative additive and is paraben-free, however, the starting material (i.e., 1-octene) is derived from fossil-based (petrochemical) resources and, importantly, represents a non-renewable raw material, i.e., a non-sustainable resource.

[0015] Thus, as noted above, there is a need for alternative preservative systems (used alone or as part of a barrier technology), including those without parabens, that are more consumer and eco-friendly. There is also a need in the art for a material that is an alternative preservative material or can be used in an alternative preservative system that is a 100% natural and renewable ("sustainable") feedstock to produce an antimicrobial agent that can be used as or in an alternative preservative system. Examples of "natural" antimicrobial agents are those made from biologically derived raw materials (e.g., from current and sustainable agricultural activities, such as non-GMO-based fermentation, algae, plant-derived, or vegetable-derived, such as antimicrobial agents made from vegetable sources or biomass. They are not petrochemically derived (e.g., derived from sustainable tree and plant farms active in the 21st century). Such raw materials are referred to herein as "natural" and "renewable" (i.e., "sustainable"), and are referred to as non-petroleum-derived raw materials. In addition, such materials are formed from "new" carbon, rather than from petroleum or other fossil fuel sources ("old" carbon). These products are referred to herein as "natural" products, and are referred to in the art as non-petrochemically derived or "bio" products. By "sustainable" herein, applicants refer to materials from renewable sources, rather than materials that deplete limited natural resources such as fossil fuels or other non-renewable resources such as petroleum. Therefore, natural or bio products that are non-petrochemically derived and / or made from non-petrochemically derived sources will be sustainable and renewable.

[0016] True natural products (biocompounds) are formed using biomass (e.g., materials stored by carbon cycle processes in living plants and roots, etc., or released by animal respiration or by decomposition). When carbon breaks down and breaks down under pressure over millions of years, it produces fossil fuels (the source of petrochemically derived carbon). Biocompounds herein are intended to include materials derived from carbon of plant sources / biomass, which are recent and also sustainable, and are not derived from fossil fuels.

[0017] These bio-based or "natural" raw materials can be used to produce alternative preservative preparations. Bio-based or "natural" products from these raw materials can be tested to determine that they come from real, natural and sustainable (as those terms are defined in this article) raw material sources. Some products are widely known or advertised for their natural origin, but in fact the product may not be made from real natural and / or sustainable raw materials. Natural organic products are generally defined as compounds naturally produced by living organisms. In order to distinguish petroleum-based products from truly natural and / or sustainable products, people must use established and reliable test methods to test authenticity. The most commonly used method is to use mass spectrometry to analyze stable isotopes in detail and evaluate carbon-12 / carbon-13 and / or hydrogen-1 / hydrogen-2 ratios. This test is available through several analytical service testing organizations, and compared with radiocarbon testing methods, this test is faster, more cost-effective, and more detailed information can be obtained.

[0018] Stable isotope analysis is based on the principle of the kinetic isotope effect. The latter effect is well known to those skilled in the art of chemical kinetics. In the broadest sense, heavy isotopes of a particular element react slower than their lighter equivalents (e.g., carbon-12 compared to carbon-13). Therefore, when plants incorporate carbon dioxide into their biomass, the ratio of carbon-12 to carbon-13 will vary depending on the type of chemistry used in the plant to make the biomass (e.g., whether the plant undergoes a C3 or C4 photosynthesis pathway). This is usually reported as δ 13 C / 12 C ratio (i.e., δ 13 C), and is known as the current CO2 standard. In addition, similar isotopic kinetic effects are observed when water is incorporated into nascent biomass, and this is measured as δ 2 H / 1 H ratio (i.e., δ 2 H) Use δ 13 C and δ 2 By combining the H ratios, a person skilled in the relevant art can readily distinguish and verify the nature of the raw material used to prepare the product to be analyzed (i.e., whether it is petrochemically derived or derived from recently living or living algae, plants or similar biological sources).

[0019] exist Figure 2 In the Figure 1, one can generally see how isotope ratios can be used to determine the origin of various detergents that are strongly correlated with the raw materials described herein, such as 1-octanol. Figure 2 In the curve diagram, δ 2 The H value more clearly defines the difference between petroleum-based feedstocks and renewable feedstocks, so in this case, it is comparable to δ 13 Compared with the C value, it has a greater value and typicality.2 H and δ 13 The combined use of C values ​​is actually the preferred technique of the present invention for demonstrating that a feedstock is natural and renewable.

[0020] Radiocarbon is an unstable isotope of carbon called 14 C. 14 C is an unstable isotope that emits radiation energy in the form of beta particles at a very consistent rate and eventually decays to the more stable 14 N (i.e., radiocarbon half-life is 5730 years). Because petroleum-based (i.e., petrochemically derived) feedstocks are derived from plants and animals buried millions of years ago, the radiocarbon (i.e., 14 C) has ceased to decay. ASTM International provides a test standard to determine the authenticity of "biobased compounds" using radiocarbon, which can be found in ASTM D6866-16. This standard distinguishes newer carbon from carbon derived from fossil fuels, or from petroleum and petrochemical-derived sources (i.e., "old carbon"). 14 The amount of C is known, so the percentage of carbon from renewable sources can be estimated from total organic carbon analysis, which provides the data necessary to determine whether the compound is truly derived from a "natural" and / or "sustainable" ("renewable") raw material source, or, on the contrary, derived from an "old" buried (i.e., petrochemically derived or petroleum-based source) compound. The use of petroleum-based or generally labeled fossil-based raw materials is generally considered to be unsustainable, i.e., old carbon is unsustainable and not a renewable raw material, and is also not considered to be "natural" and "sustainable" in the art. As defined herein, it will not be considered to be a "natural" product or to be used in a "natural" preparation. Therefore, the use of such raw materials does not represent a way to develop a "natural" and "renewable" alternative preservative.

[0021] Dehydrating terminal alcohols to form olefin starting materials using conventional methods chemically produces a mixture of 1-olefins, 2-olefins, and 3-olefins due to rearrangement and migration of 1-olefin products during the dehydration process. Using this mixture of olefins, which is ultimately dihydroxylated to provide a mixture of diols, results in low yields of the desired terminal 1,2-diol material and undesirable contaminants.

[0022] In one known pathway to form caprylyl glycol (1,2-octanediol) starting from 1-octanol made from petrochemically derived (i.e., petroleum-derived or fossil fuel-derived) feedstocks, the following reaction is known to occur:

[0023]

[0024] Table A

[0025]

[0026]

[0027] As can be seen from the above reaction scheme, 1-octanol is converted into olefins, i.e. octenes, using heat and traditional acid catalysts. The acid sites exposed in the catalyst allow the thermodynamically more stable 2-octenes to form together with 1-octenes. The 2-octenes regioisomers formed (comprising 3-octenes and 4-octenes (not shown) as shown above) are very difficult to separate from 1-octenes and provide the lower net chemical yield of the desired 1-octenes. Therefore, increasing or higher regioselectivity is the key factor that the catalytic dehydration of 1-octanol becomes 1-octenes, and is the target that is desired to be reached in the related art. When using renewable and natural raw materials, the key is the reaction efficiency (i.e. chemical yield) of the desired product (i.e. 1-olefins). Still need the high regioselectivity dehydration of 1-octanol in this area, it also has the high chemical conversion rate of using effective process equipment and operating in a fast and energy-saving manner.

[0028] Therefore, the traditional route to the desired terminal 1,2-octanediol using a mixture of regioisomers as shown above is reduced and the yield is also reduced. This makes the ability to chemically form the desired alternative preservative material insufficient and lacks cost advantages, resulting in more waste in the process and making the overall process less sustainable. There is a strong need in the art for a process with high regioselectivity and high chemical conversion rate for the production of bio-1-octenes from bio-1-octanol.

[0029] International Patent Publication No. WO 2004 / 078336 A2 uses gamma-alumina without additional cocatalysts, but rather gives it very large pores and volume to enhance the regioselectivity of 1-octanol dehydration. The regioselectivity of octenes in this study was high (97.7%), but the chemical conversion was 65% and the product selectivity was only 25%. Therefore, the chemical yield of 1-octenes from 1-octanol using this catalytic system was only about 15.9%.

[0030] In another example, the formation of 1-octene by cracking ether derivatives of 1-octanol is described in U.S. Patent No. 7,576,250 B2. In this patent, 1-octanol must first be converted into methyl ether (i.e., methyl octyl ether), which is then subjected to and passed through a γ-alumina catalyst. This involves additional chemicals and additional costs to make ether, and methanol is lost in this process, resulting in an extremely ineffective and atomically inefficient process. Most notably, the catalyst starts with good conversion and regioselectivity in the first few hours, and then, only within a run time "TOS" of just 20 hours, all catalysts disclosed in the art show a consistent and significant decrease in chemical conversion, with a loss of regioselectivity. Such short catalyst life is unacceptable in commercial production.

[0031] Leaded alumina catalysts are described in Chinese Patent No. 105312044 B, in which lead salt pseudoboehmite shows high apparent selectivity and conversion. The carbon deposition rate of this catalyst is about 0.04% / h, which is extremely unfavorable and unsatisfactory in continuous operation of about 1000 hours. Further limiting is that these catalysts are doped with toxic heavy metals, namely lead. If used for commercial production on an industrial scale, the use of these catalysts will require expensive environmental control and artificial safety precautions.

[0032] One approach to making "natural" alkanediols is by fermenting biomass to form straight-chain, linear alkanediols. For example, U.S. Patent Application Publication No. 2005 / 0069997 A1 teaches the formation of 1,3-propanediol from a fermentation broth. However, 1,3-propanediol is not a 1,2-alkanediol. Fermentation processes to form long-chain diols are chemically inefficient (i.e., poor life-cycle-assay numbers) and additionally require the use of GMO-bacteria or GMO-yeast, especially if one attempts to make long carbon 1,2-alkanediols.

[0033] Another example of natural bio-alcohol described in the art is bio-1-butanol, which is a known substance used for commercial production since the acetone-butanol-ethanol fermentation process carried out by anaerobic Clostridium sporogenes (a non-transgenic bacteria) was discovered by Pasteur in 1862, although its current usage is very limited. These bacteria ferment both C5 and C6 sugars to form a mixture of acetone, 1-butanol and ethanol (i.e., ABE). Since the discovery of ABE, the progress of fermentation technology can provide bio-1-butanol production that is better than acetone and ethanol production. Although the output is improved, it is still difficult and energy consumption is large to purify bio-1-butanol from other impurities such as ethanol and acetone involved in the fermentation liquid and fermentation process. In addition, it is not clear to the applicant that non-transgenic bacteria or yeast processes can form longer chain alcohols (i.e., 6 or more chains, such as 1-hexanol or 1-octanol).

[0034] Bio-1-butanol is known to be a source for making biofuels and provides a way to convert straight-chain, linear, four-carbon primary alcohols into bio-1-olefins at very high yields to increase the production of biofuels and can also be used, for example, to produce environmentally friendly tires. In this method, bio-1-alcohol is dehydrated to bio-1-olefins with high selectivity and chemical yield. The resulting bio-1-olefins can be used to prepare high-flash point diesel and jet biofuels that can be used for civilian and military purposes. Bio-1-butanol is dehydrated using a solid phase dehydration catalyst, which includes an inorganic support, such as gamma-alumina or zinc aluminate (ZnAl2O4), and has been treated / modified with an alkaline aqueous solution. The support can be further treated with an organosilane diluted in at least one hydrocarbon solvent. The method can convert bio-1-butanol in a fermentation process containing 0.1 to about 90 wt% water and produce the corresponding 1-olefins with a regioselectivity of 92 to 99%, and only one pass through the solid phase catalyst can produce bio-1-butene with a reaction conversion rate of greater than 95% and a chemical yield of greater than 90%. However, even for this result for bio-1-butene, it should be noted that the conversion of 1-octanol to 1-octene is not a simple analogy of the conversion of 1-butanol to bio-1-butene. In fact, the comparative example below shows that silanization of the catalyst leads to a loss of regioselectivity in the 1-octanol dehydration chemistry.

[0035] Based on the above, while progress has been made, there is a need in the art to continue to improve consumer products such as personal care products, household products, industrial products, and pharmaceutical products to provide additives, particularly for antimicrobial agents, or to enhance the effectiveness of known preservatives or alternative preservative systems, so that the products are free from contamination and remain fresh during storage and use, while avoiding the use of traditional preservatives, and to find and rely on components of consumer product compositions from natural biological sources. More particularly, there is a need for natural and preferably renewable / sustainable feedstock sources to produce natural, bio-caprylyl glycol (i.e., natural or bio-1,2-octanediol) and related bio-1-olefin intermediates. Summary of the invention

[0036] The present invention provides an effective way to obtain 100% "natural" or "biocompounds" which are truly "natural" materials and preferably include bio-1,2-alkanediols having a carbon length of about 5 to about 20, preferably about 5 to about 14, which can be used alone, in combination with different types of bio-1,2-alkanediols, or mixed with other natural or traditional antimicrobial agents and other cosmetic additives.

[0037] The present invention includes a process for synthesizing bio-1,2-alkanediols, comprising: providing a bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%; and converting the bio-olefin to a bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms.

[0038] In one embodiment of the process, the bio-olefin and the bio-1,2-alkanediol each have a carbon chain length of about 6 to about 14 carbon atoms. The bio-olefin and the bio-1,2-alkanediol each may have a carbon chain length of about 6 to about 10 carbon atoms. The bio-olefin and the bio-1,2-alkanediol each may have a carbon chain length of about 6 to about 8 carbon atoms. For example, the bio-olefin may be bio-octenes and the bio-1,2-alkanediol may be bio-1,2-octanediol.

[0039] In another embodiment of the process, the bio-olefin is preferably produced by a process in which the bio-1-ol is dehydrated by heating the bio-1-ol in a reactor having a catalyst. The reactor may be a fixed bed reactor. The fixed bed reactor may also be, for example, a fluidized fixed bed reactor. In such an embodiment, the catalyst may be selected from ZnAl2O4 and gamma-alumina catalysts.

[0040] In preferred embodiments, the bio-olefins have a bio-1-olefin regioselectivity of about 92% to about 99%, preferably about 95% to about 99%. The process also preferably produces at least about 92% to about 99% bio-1,2-alkanediol.

[0041] As described above, in one embodiment, a catalyst treatment may be employed. The catalyst may be a gamma-alumina catalyst treated with an alkali to form a modified gamma-alumina catalyst. The alkali may include a Group I or Group II metal. The gamma-alumina catalyst may be treated with a calcium promoter, for example, to provide a modified gamma-alumina catalyst. The modified gamma-alumina catalyst may then be calcined to provide a calcined gamma-alumina catalyst. In one embodiment, where a calcium promoter is used, the calcium promoter may be used in an amount of about 0.01 wt% to about 4 wt% based on the weight of CaO measured after calcination, and is preferably used in an amount of about 1 wt% to about 2 wt% based on the weight of CaO measured after calcination.

[0042] The preferred temperature during calcination is about 400° C. to about 500° C., more preferably about 420° C. to about 480° C., and most preferably about 440° C. to about 460° C. Calcination can be carried out in an oven. Calcination can be performed in air or under an atmosphere of nitrogen or other inert gas.

[0043] Before converting the bio-olefin to bio-1,2-alkanediol, the bio-olefin is preferably subjected to a distillation step to purify the bio-olefin. The bio-1,2-alkanediol formed from the bio-olefin may also be subjected to a final distillation step to purify the bio-1,2-alkanediol.

[0044] In another embodiment of the process, bio-olefins may be produced by a process wherein the bio-1-ol in water is dehydrated by heating the bio-1-ol with a catalyst without or with a purge gas. The purge gas may preferably be nitrogen, but other inert gases may be used within the scope of the present invention.

[0045] The bio-olefin in the process can also be converted into bio-1,2-alkanediol by reacting the bio-olefin in the presence of at least one of a peroxy acid (e.g., formic acid or acetic acid) and hydrogen peroxide to form a mixture of bio-1,2-epoxyalkanes having an epoxy ring and bio-1,2-alkanediol, and contacting the mixture with water and sodium hydroxide to completely form bio-1,2-alkanediol.

[0046] The overall process preferably produces at least about 60% to about 99% bio-1,2-alkanediol, and more preferably produces at least about 72% to about 99% bio-1,2-alkanediol.

[0047] The present invention also includes a process for preparing bio-1,2-alkanediol, comprising: providing a bio-1-ol and a catalyst treated with a base; dehydrating the bio-1-ol in the presence of the catalyst to form a bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%; and converting the bio-olefin to a bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms. Preferably, the catalyst is treated with a promoter and then calcined.

[0048] The catalyst in the process may also be a gamma-alumina catalyst, and the base may include calcium. The gamma-alumina catalyst is preferably treated with a calcium promoter and calcined at a temperature of about 400° C. to about 500° C. after treatment. The process preferably produces about 92% to about 99% bio-1,2-alkanediol.

[0049] The present invention also includes a method for treating a catalyst for alcohol dehydration, comprising providing a gamma-alumina catalyst; treating the gamma-alumina catalyst with a base comprising a Group I or Group II metal, preferably a promoter as described herein; and heating the gamma-alumina catalyst to a temperature of about 400°C to about 500°C, preferably in an extremely controlled and careful manner. The base may include calcium, and preferably the base may be a calcium promoter and the heating is performed during calcination. The calcium promoter may be used in an amount of about 0.01 wt% to about 4 wt% based on the weight of CaO measured after calcination, more preferably in an amount of about 1 wt% to about 2 wt% based on the weight of CaO measured after calcination, preferably after careful calcination. In a preferred embodiment, the temperature during calcination may be about 420°C to about 480°C, and more preferably may be about 440°C to about 460°C. Beneficial results are achieved based on the applicant's process including the preferred ranges indicated. The applicant judges that high calcination temperatures reduce the catalyst regioselectivity and thus reduce the chemical yield of bio-1-olefins.

[0050] The present invention further includes a composition comprising at least one first bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms synthesized by converting a first bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%.

[0051] The composition may be a personal care composition, such as a hair care composition, an oral care composition, a skin care composition, or a cosmetic composition.

[0052] The composition may also be a composition for household products such as fabric care products or cleaning products.

[0053] The composition may also be an industrial composition, or a pharmaceutical composition, a vitamin composition, or a health care composition.

[0054] In one embodiment of the composition of the present invention, the composition may include a second bio-1,2-alkanediol different from the first bio-1,2-alkanediol, the second bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms, synthesized by conversion of a second bio-olefin, preferably regioselectively synthesized, such that the resulting bio-olefin of about 5 to about 20 carbon atoms has a terminal bio-olefin content of at least about 80% and a bio-1-olefin regioselectivity of at least about 80%. The composition may include at least one other biocompound different from the first and second bio-1,2-alkanediols. In another embodiment, the composition may include an antimicrobial compound different from the first and second bio-1,2-alkanediols and different from the other biocompounds. The composition may also include at least one other biocompound different from the at least one bio-1,2-alkanediol, and in another embodiment, such a composition may also include at least one antimicrobial compound different from the at least one bio-1,2-alkanediol and different from the other biocompounds. The first bio-1-olefin in the composition preferably has a regioselectivity of about 92% to about 99%, more preferably about 95% to about 99%. The first bio-olefin may be bio-octene and the at least one first bio-1,2-alkanediol may be bio-1,2-octanediol.

[0055] The present invention also includes a method of providing an antimicrobial effect to a composition comprising incorporating an antimicrobial system into the composition, wherein the antimicrobial system comprises at least one first bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms synthesized by converting at least one first bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and at least about 80% bio-1-olefin regioselectivity. The antimicrobial system may further comprise a second bio-1,2-alkanediol different from the first bio-1,2-alkanediol, wherein the first bio-1,2-alkanediol has a carbon chain length of about 5 to about 20 carbon atoms and is formed by regioselectively converting a second bio-olefin different from the first bio-olefin, the second bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and at least about 80% bio-1-olefin regioselectivity. The composition may further comprise at least one other biocompound different from the first and second bio-1,2-alkanediols, and in another embodiment may comprise at least one other preservative compound different from the first and second bio-1,2-alkanediols and different from the other biocompounds. Such compositions may also include at least one other biocompound different from the at least one first bio-1,2-alkanediol. The antimicrobial agent may also include at least one other antimicrobial compound and / or preservative compound different from the at least one first bio-1,2-alkanediol and different from the other biocompounds. The antimicrobial system may be manufactured to exhibit antimicrobial efficacy. The first bio-1-olefin preferably has a regioselectivity of about 92% to about 99%, and preferably about 95% to about 99%. The first bio-olefin may be bio-octenes and the at least one first 1,2-alkanediol may be bio-1,2-octanediol.

[0056] In one embodiment, the present invention also includes a method of enhancing the antimicrobial efficiency of an antimicrobial and / or preservative in a composition, comprising incorporating an antimicrobial system into the composition, wherein the second antimicrobial system comprises at least one first bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms, synthesized by regioselective conversion of a first bio-olefin having a carbon chain of about 5 to about 20 carbon atoms and at least about 80% bio-1-olefin regioselectivity. In the method, the antimicrobial system may further comprise a second bio-1,2-alkanediol different from the first bio-1,2-alkanediol, wherein the second bio-1,2-alkanediol has a carbon chain length of about 5 to about 20 carbon atoms and is formed by converting a second bio-olefin different from the first bio-olefin, the second bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and at least about 80% bio-1-olefin regioselectivity. In the composition, it may further comprise at least one other bio compound different from the antimicrobial and / or preservative and different from the first and second bio-1,2-alkanediols. The composition may further include at least one other biocompound different from the at least one first bio-1,2-alkanediol. The first bio-1-olefin preferably has a regioselectivity of about 92% to about 99%, and more preferably about 95% to about 99%. In one embodiment, the antimicrobial system exhibits antimicrobial efficacy. The first bio-olefin may be bio-octenes, and the at least one first bio-1,2-alkanediol may be bio-1,2-octanediol.

[0057] In another embodiment, the present invention includes an antimicrobial product comprising at least one first bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms synthesized by conversion of a first bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%. The product may further include a second bio-1,2-alkanediol different from the at least one first bio-1,2-alkanediol, the second bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms and formed by conversion of a second bio-olefin different from the first bio-olefin, the second bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%.

[0058] The antimicrobial product may further include at least one other biocompound different from the at least one first and second bio-1,2-alkanediols. In one embodiment, the product may further include a second antimicrobial agent and / or preservative different from the antimicrobial product. The product may also include at least one other biocompound different from the at least one first bio-1,2-alkanediol, and may also include a second antimicrobial agent and / or preservative different from the antimicrobial product. The first bio-1-olefin preferably has a regioselectivity of about 92% to about 99%.

[0059] The antimicrobial product preferably also exhibits antimicrobial efficacy.The first bio-olefin may be bio-octene and the at least one first 1,2-alkanediol may be bio-1,2-octanediol.

[0060] The present invention also includes a product for enhancing the efficacy of an antimicrobial and / or preservative in a composition, the product comprising at least one first bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms, synthesized by conversion of a first bio-olefin having a carbon chain of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%. Such a product may further include a second bio-1,2-alkanediol different from the at least one first bio-1,2-alkanediol, the second bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms and formed by conversion of a second bio-olefin different from the first bio-olefin, the second bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%. The composition of the product may also include at least one other biocompound different from the at least one first and second bio-1,2-alkanediols, and may also include at least one other biocompound different from the at least one first bio-1,2-alkanediol. The first bio-1-olefin preferably has a regioselectivity of about 92% to about 99%. The first bio-olefin may be bio-octenes, and the at least one first bio-1,2-alkanediol may be bio-1,2-octanediol. The product preferably exhibits antimicrobial efficacy. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] The foregoing summary of the invention and the following detailed description of preferred embodiments of the invention will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, presently preferred embodiments are shown in the accompanying drawings. However, it should be understood that the invention is not limited to the precise arrangements and instrumentalities shown. In the accompanying drawings:

[0062] Figure 1 is a process flow diagram of the steps in a preferred embodiment of the method herein;

[0063] Figure 2 It is the delta-value of petroleum-based alcohols, olefins and acids and their corresponding natural and renewable analogs.2 H and δ 13 Graphical representation of C value;

[0064] Figure 3 is a gas chromatography (GC) chromatogram of products produced from a reactor for dehydrating bio-1-octanol using the catalyst prepared in Example 4 with 0.2 ml of bio-1-octanol fed and heated to 315° C.;

[0065] Figure 4 is the GC chromatogram of bio-1-octene obtained from the reactor after distillation;

[0066] Figure 5 is a GC chromatogram of bio-1,2-octanediol obtained by dehydrating bio-1-octene to 1,2-octanediol and then fractionating 1,2-octanediol;

[0067] Figure 6 is the GC chromatogram of petroleum-1,2-octanediol currently approved for use in cosmetic preparations; and

[0068] Figure 7 These are comparison photos of the catalyst after 1400h of TOS (left) and the new catalyst (right). DETAILED DESCRIPTION

[0069] The present invention includes processes for synthesizing bio-1,2-alkanediols. As used herein, "bio" when used with "alkanediols" or any specific alkanediol compound referred to within such compounds, as described above, is intended to mean that the compounds within such compounds, preferably all carbons in the compounds, as further described below, are "natural" compounds, which are also truly natural compounds derived from plant sources (algae, plants, animals or biomass derived), and are non-petrochemically derived (i.e., not derived from non-renewable resources such as fossil fuels, petroleum or other "old" carbon sources). In this sense, they are also sustainable compounds because they are derived from renewable materials. This also means that such materials are formed from bio-olefins. When used in the terms "bio-alcohols" or "bio-olefins" and similar compounds herein, "bio" also refers to having the same meaning as above with respect to describing "bio-1,2-alkanediols". Such materials should preferably meet the following requirements: they can be confirmed to have and be derived from real or "new" carbon material (non-petrochemically derived) feedstocks by testing such compounds using existing methods such as mass spectrometry and / or gas chromatography as described above, the current ASTM D6866-16 standard, or specific stable isotope analysis (CSIA). The present invention also includes bio-1-olefins and bio-1,2-alkanediols obtained from synthetic processes, and various products including them. The present invention further includes a method for treating a catalyst, which can be used in embodiments herein to dehydrate bio-1-ols to form bio-olefins, which are used in the processes herein to form bio-1,2-alkanediols.

[0070] The present invention provides an efficient route to 100% "natural" or "bio" compounds that are derived from non-petrochemically derived new carbon or real carbon materials and are preferably used in compositions and products that can be used in a variety of end uses and compositions, including as a component of antimicrobial compositions and as a cosmetic additive, as well as other uses described herein.

[0071] Also disclosed herein is a method of using bio-1,2-alkanediol as an antimicrobial agent in a composition (e.g., in an alternative preservative system or used with an alternative preservative system) and / or as a barrier technology. Various compositions comprising bio-1,2-alkanediol are also disclosed, including when used as an antimicrobial agent. Methods of enhancing the antimicrobial efficacy of a composition that already includes a preservative or an alternative preservative system and the resulting enhanced antimicrobial efficacy composition are also described. Each of these methods includes incorporating bio-1,2-alkanediol, a combination of at least two different bio-1,2-alkanediols, or at least one bio-1,2-alkanediol and at least one other biocompound different from at least one bio-1,2-alkanediol into a composition, wherein the bio-1,2-alkanediol acts as an antimicrobial agent or improves the efficacy of another antimicrobial agent, preservative, or other alternative preservative system already present in the composition. Bio-1,2-alkanediol itself can be an antimicrobial product and / or an antimicrobial efficacy-enhanced product, whether used alone; in combination with one or more different bio-1,2-alkanediols; or in combination with one or more different bio-1,2-alkanediols and at least one other biocompound different from bio-1,2-alkanediol and / or optionally, a different antimicrobial agent, preservative or alternative preservative system. When used in the compositions herein, bio-1,2-alkanediol exhibits antimicrobial efficacy.

[0072] In one embodiment herein, a process for synthesizing bio-1,2-alkanediol is described herein. As above, materials referred to herein as "natural" are intended to include non-petrochemically derived and sustainable materials, whether synthesized from non-petrochemically derived natural materials, or formed from natural, preferably authentic natural or bio-based sources.

[0073] The method includes providing a bio-olefin having a carbon chain of about 5 to about 20 carbon atoms, preferably about 6 to about 14 carbon atoms, and more preferably about 6 to about 10 carbon atoms, wherein bio-1-octene is preferred. The bio-olefin is preferably a bio-1-olefin having a traditional alpha-olefin structure. It is also preferably prepared with a regioselectivity of at least about 80%, more preferably at least about 92%, and most preferably at least about 95% to as much as 99%.

[0074] Such bio-olefins may be bio-1-pentene, bio-1-isopentene, bio-1-hexene, bio-1-heptene, bio-1-octene, bio-1-nonene, bio-1-decene, bio-1-dodecene, and related bio-1-olefins of chain length up to 20 carbons. Larger or smaller bio-olefins may also be prepared, however, preferred bio-olefins for use herein are those having sufficient chain length to serve as effective antimicrobial agents without loss of desired properties when converted to bio-1,2-alkanediols. Such bio-olefins may be linear or branched chain molecules, although linear molecules are preferred and may include one or more functional or substituted groups for the desired end effect in the end use application, such as sulfonic acid groups, hydroxyl groups, ether groups, amide groups, carbonyl groups, carboxylic acid groups, amine groups, fluorinated groups, aryl or aromatic hydrocarbon groups, and similar functional groups, without intending to be limiting. It is preferred that any such functional or substituent groups do not interfere with the conversion to the alkanediol or with the desired antimicrobial end use application of the particular alkanediol.

[0075] Such bio-olefins (such as bio-1-hexene and bio-1-octene) as produced in accordance with the present invention can be used to make bio-1,2-alkanediols as described herein, and can also be used to make other bio-based compounds and polymers including, for example, for synthesizing bio-based olefin copolymers. The bio-1-olefins herein can be used, for example, in free radical or catalytic polymerization processes known in the art to produce various biopolyalphaolefin homopolymers and copolymers, which are useful as lubricants and cosmetic ingredients. Another example includes bio-linear low density polyethylene (bio-LLDPE), which can be prepared via copolymerization of bio-ethylene (derived via dehydration of sugarcane-derived bioethanol to bio-ethylene) with bio-1-olefin copolymers to produce 100% renewable bio-LLDPE, a thermoplastic resin useful in film applications such as food and non-food packaging and shrink / stretch films.

[0076] The process of the present invention includes embodiments wherein the process produces bio-1,2-alkanediols comprising providing a bio-1-ol and a catalyst treated with a base, preferably treated with a promoter, followed by calcination; dehydrating the bio-1-ol in the presence of the catalyst to form a bio-olefin having a carbon chain length of about 5 to about 20 carbon atoms and a bio-1-olefin regioselectivity of at least about 80%; and converting the bio-olefin to a bio-1,2-alkanediol having a carbon chain length of about 5 to about 20 carbon atoms.

[0077] As Figure 1 The illustrated embodiment 100 provides a general flow diagram of a preferred process for making bio-1,2-alkanediol, which incorporates a preferred method of treating the catalyst as further described below.

[0078] In the process generally referred to herein as process 100, Figure 1 In the reactor 101, a catalyst is prepared before the introduction of the bio-1-ol. A suitable gamma-alumina catalyst 110 (e.g., Al2O3) is introduced into the reactor 101, into which a calcium promoter or other base treatment material 102 as further described below is introduced. After suitable treatment as described in detail below, the modified catalyst 103 leaves the reactor 101 and enters a heating chamber 104, such as an oven for heat treatment. If a catalyst promoter is used, for example, a calcination step is performed at a preferred and controlled temperature range to increase the level of regioselectivity of the resulting bio-olefins in the next step. For example, after calcination in the chamber 104, the calcined or otherwise heat-treated catalyst 105 is introduced into the reactor 107 together with the bio-1-ol 106, such as bio-1-hexanol or bio-1-octanol, to promote intimate contact between the alcohol and the catalyst. Suitable reactors include fixed bed reactors, fluidized bed reactors, tubular reactors and other suitable reactors. After sufficient time for dehydration of the bio-1-ol to bio-olefins 109 (which are highly regioselective to bio-1-olefins), further, optional distillation or other purification or refining steps may occur in a column or other apparatus 110. The refined or otherwise purified and highly regioselective bio-olefins (which should be large amounts of bio-1-olefins) are then introduced into a reactor 112 for conversion of the bio-1-olefins to bio-1,2-alkanediol 113. This bio-1,2-alkanediol 113 may be further and optionally refined, such as by distillation in a column or by other steps in apparatus 114. After purification or distillation, a final high yield of up to 99% is removed as final bio-1,2-alkanediol 115.

[0079] The bio-1-olefins may be prepared using a catalytic process, and preferably using a catalyst that has been treated according to the methods described herein. In one embodiment, the bio-olefins are preferably prepared herein as bio-1-olefins with high regioselectivity, the bio-olefins being formed using bio-1-ols, i.e. dehydrated by heating the bio-1-ols in the presence of a catalyst. This may be done, for example, by passing the bio-1-ols through a fixed bed reactor or a fluidized bed reactor. The fixed bed may be filled with a catalyst, preferably a treated catalyst that has been treated using the following techniques.

[0080] For example, bio-1-alcohol is derived from plant sources, including biomass that can produce related acids (for example, 1-octanol can be derived from coconut, palm or other plant sources, or can produce octanoic acid biomass, which is subsequently reduced to 1-octanol via catalytic dehydrogenation). Bio-1-alcohol is then selectively dehydrated by feeding the material to, for example, a fixed bed reactor or other suitable reactor providing close contact between bio-1-alcohol and the catalyst at an elevated temperature. The fixed bed can be filled or otherwise arranged to provide sufficient contact with the catalyst. Other suitable reactors can be provided for this purpose, provided that they can achieve suitable contact that contributes to dehydration. Examples include tubular reactors, fixed beds and fluidized bed reactors, etc.

[0081] The reactor can be designed as a simple heated reaction tube filled with a catalyst and a gaseous bio-1-ol stream passed over the catalyst, preferably providing greater than about 95% conversion in a single pass, with greater than about 98% being a preferred embodiment, and in all cases without using any recycle stream in the overall process stream. In one embodiment, the reaction tube is heated isothermally, with 1 to 10 reaction zone temperatures along the length of the tube, each heated in the range of about 240°C to about 360°C to optimize catalyst performance. In a preferred embodiment, the reaction tube has 1 to 4 reaction zone temperatures in the range of about 260°C to about 340°C.

[0082] In one embodiment, the process is operated in a fluidized bed reactor at a temperature range of about 240° C. to about 360° C. Other continuous flow reactor designs may be used according to procedures and practices used by those skilled in the chemical engineering arts.

[0083] The catalyst used can be prepared by treating gamma-alumina (e.g., ) to produce a second catalyst. The second catalyst is then calcined to produce a third catalyst. It has been found that the calcination temperature is the most unexpected and critical to producing the most effective catalyst. As shown below, when calcined at about 500°C, the regioselectivity is significantly reduced compared to catalysts calcined at lower temperatures. In one embodiment, as shown in Table 1 below, the preferred calcination temperature is from about 400°C to about 480°C, and the more preferred calcination temperature is from about 440°C to 460°C.

[0084] Table 1

[0085]

[0086] Different catalysts can be used to assist the bio-1-ol in the dehydration step. However, it is preferred to use a suitable catalyst that can achieve a high level of regioselectivity as described herein. Suitable catalysts include γ-alumina based catalysts and ZnAl2O4. Preferably, the catalyst is treated with a base such as sodium hydroxide, potassium hydroxide, calcium acetate, etc. In a preferred example, the catalyst is a γ-alumina catalyst treated with a base including a Group I or Group II metal. In a more preferred embodiment, calcium can be included in the base and the calcium promoter used. After treatment with the calcium promoter to form a modified γ-alumina catalyst, in a further preferred embodiment, the modified γ-alumina catalyst is then calcined using different calcination techniques but preferably at a temperature much lower than that used in the standard calcination method to provide a calcined γ-alumina catalyst. This initial treatment provides a modified γ-alumina catalyst, which is then calcined to prepare for use in different processes, including in the dehydration step of the process herein for preparing bio-1-olefins and their subsequent conversion into bio-1,2-alkanediols.

[0087] When a calcium promoter is used, it can be used in the above treatment in an amount of about 0.01 wt% to about 4 wt% based on the amount of CaO measured after calcination. In a preferred embodiment, about 1 wt% to about 2 wt% of the calcium promoter is used based on the amount of CaO measured after calcination.

[0088] In another embodiment, if desired, the alumina-based treated catalyst can be organosilylated by further treating with an organosilane, such as diethoxydiphenylsilane, to form an organosilylated base-treated gamma-alumina catalyst. The organosilylation base can be, for example, diethoxydiphenylsilane, dichlorodiphenylsilane, and similar materials.

[0089] In one embodiment, the catalyst support may include ZnAl2O4 and may also be modified by a base, such as by reaction with a co-catalyst, and similar catalysts and modified catalyst materials known or to be developed may also be used, which are capable of performing the process described herein in a manner similar to the catalysts mentioned herein that are capable of producing high levels of regioselectivity.

[0090] Catalyst as above can also be processed alternatively or with organosilane or organosilane modified material, to produce the catalyst modified by promoter, except being applicable to alkali treatment.By processing with diethoxydiphenylsilane, this promoted catalyst can further carry out organosilylation with organosilane, generates the gamma-alumina catalyst of the third organosilylation and promoter modification.The organosilane used for modified catalyst can be for example diethoxydiphenylsilane, dichlorodiphenylsilane and similar materials.As seen in this paper embodiment 10, the silylation of catalyst causes the reduction of bio-1-octene selectivity, shows again the difference with the prior art and the necessary dehydration catalyst composition of the high regioselectivity of 1-butanol or 1-octanol directly and the difference confirmed.

[0091] In other treatment techniques herein, the gamma-alumina catalyst can be modified by the technique of incipient wetness impregnation. A solution of an alkali is used to modify the solid support in a manner that avoids excess moisture that may cause damage to the support and chemical changes. In one embodiment, the incipient wetness impregnation solution (IWS) is about 40% to about 100% by weight of the solid support, which can be, for example, an untreated gamma-alumina catalyst. In one embodiment, the untreated gamma-alumina catalyst is selected from commercially available Preferably, the IWS is from about 50% to about 60% by weight of the catalyst support.

[0092] γ-alumina can also be used in a range of about 50 to about 400 m 2 / g of surface area of ​​the powder form. In one embodiment, the gamma-alumina is formed by a suitable extrusion process, which is known to those skilled in the art of solid phase catalysts. In one example, the gamma-alumina is in the form of a 1 / 16'' to 1 / 8'' cylindrical rod with an aspect ratio of about 20: 1, preferably about 5: 1. The extrudate can be in the shape of a sphere, star, hollow cylinder, or any three-dimensional shape that can ultimately deliver gamma-alumina with sufficient surface pore volume, mechanical strength and physical size for use in a continuous flow reactor system.

[0093] Once prepared, e.g., as described above, the preferably promoter-treated gamma-alumina catalyst, e.g., base-treated, is preferably calcined at carefully regulated temperatures. This is conducted at elevated temperatures, preferably in a suitable chamber such as an oven, and the temperature range is not as high as the calcination treatments typically used in prior catalyst processes when elevated to heat the material. Instead, the calcination temperature is maintained at about 400°C to about 500°C, preferably about 420°C to about 480°C, and most preferably about 440°C to about 460°C. Typically, previous standard calcination treatments were conducted at temperatures of 500°C or higher with no written or explicit limitations on effectiveness. However, applicants have discovered that by controlling this temperature and in the specific catalyst treatment process herein, when the resulting calcined catalyst resulting from the combination of catalyst treatment and carefully controlled calcination process is used to dehydrate bio-1-ols, the regioselectivity can be unexpectedly adjusted to greatly favor the formation of bio-1-olefins.

[0094] In the dehydration step herein, bio-1-alcohol can be fed to the reactor undiluted or in water through the reactor. An optional inert gas (e.g., nitrogen) can be used as a purge gas to maintain consistency and avoid contamination in the process. Although the temperature is adjusted for different bio-1-alcohols according to the reaction time and flow rate, the selected catalyst and the desired result, the bio-1-alcohol is preferably fed at a temperature of about 200° C. to about 400° C., for example, by a pump (e.g., HPLC pump) or a pressurized gas source. When the product is removed from the reactor, it is preferably monitored to determine the content, the identification of the product, and the conversion ratio and regioselectivity of the bio-1-olefin. In a preferred embodiment, the bio-1-olefin has a regioselectivity of at least about 80%, more preferably about 92% to about 99%, and even more preferably about 95% to about 99%.

[0095] In one embodiment, the Figure 1 The dehydration process described in the foregoing using the catalyst of the present invention (i.e., the catalyst obtained by the preferred treatment and calcination process described above) is carried out, and the catalyst is maintained under an inert gas flow for an extended period of time. The shutdown period can be several hours, several days or several weeks, during which heating or no heating is applied. The catalyst of the present invention can be reheated and the dehydration process resumed without any deleterious effect on catalyst activity or regioselectivity. Therefore, the catalysts of the present invention are not only durable in continuous operation, but when they are put back on line, they can withstand a rest period (deactivation) without negatively affecting the performance of the catalyst.

[0096] Bio-1-olefins may also be formed using a process in which the bio-1-ol in water is dehydrated by heating the bio-1-ol with a catalyst in a bulk process or other continuous reactor under a purge gas as above. Base treatment and optional organosilane treatment may also be used with the catalysts and reaction conditions as above, and most preferably by using a calcined gamma-alumina catalyst formed by the process described above.

[0097] Bio-1-ol can also be formed using a process in which bio-1-ol in water is dehydrated by heating the bio-1-ol with a catalyst in the bulk process or some other continuous reactor under a purge as above. Base treatment and optional organosilane treatment can also be used with catalysts and reaction conditions as above.

[0098] Once the bio-1-ols are dehydrated to form the highly regioselective end product, i.e., bio-1-olefins, the material is then converted to bio-1,2-alkanediols having carbon chain lengths of about 5 to about 20 carbon atoms. Prior to conversion, the bio-1-olefins may optionally be further refined, such as by distillation, vacuum distillation, fractionation, or similar refining steps to further purify the bio-olefins to remove trace impurities and minor undesirable fractions. For example, in forming bio-1-octene, a C8 olefin content of about 90 wt% to about 99 wt% may be achieved, and at least about 95 wt%, preferably about 97 wt% or more of the C8 olefins in the form of n-alpha-olefins (i.e., 1-octene) may be achieved. Additionally, in forming bio-1-hexene, a C6 content of about 95 wt% to about 99.8 wt% may be achieved, of which at least about 96 wt% to about 99 wt% have a 1-hexene structure.

[0099] Various chemical reactions can be used to carry out this conversion, as is known in the conversion of standard olefins to alkanediols using petrochemically derived starting materials, and / or chemical reactions for shorter chain bio-olefins. For example, the bio-1-olefins are reacted in the presence of at least one of formic acid or acetic acid and a peroxide such as hydrogen peroxide to form an intermediate solution including bio-1,2-epoxyalkanes, bio-1,2-alkanediols, and other components. This is then further contacted with an alkaline solution such as sodium hydroxide or another suitable alkaline solution to complete the formation of bio-1,2-alkanediol. The above process preferably produces about 60% to about 99%, more preferably about 70% to about 99% or about 75% to about 99% bio-1,2-alkanediol.

[0100] According to other previous techniques, bio-1-alkanol can also be converted to bio-1-olefin for use in the process by dehydrating the bio-1-alkanol using heat and an acid catalyst.

[0101] Bio-1,2-alkanediols having a chain length of about 5 to about 20 carbon atoms are synthesized by converting a first bio-olefin having a carbon chain of about 5 to about 20 carbon atoms and at least about 80%, more preferably 92% to about 99%, and most preferably about 95% to about 99% bio-1-olefin regioselectivity. In one embodiment, the bio-1-alkanol having a carbon chain of about 5 to about 20 carbon atoms is preferably first regioselectively converted to a bio-olefin such that the resulting bio-olefin contains at least about 80% or more bio-1-olefin content as above. The bio-1-olefin is then converted to 1,2-alkanediol by any known method known in the art. The bio-1,2-alkanediol obtained after the conversion can be further refined, for example, by distillation, vacuum distillation, fractionation, or other similar steps described above for refining the bio-1-olefin to provide a refined final bio-1,2-alkanediol.

[0102] Preferably, the resulting bio-1,2-alkanediol having a carbon chain of about 5 to about 20 carbon atoms is synthesized by first dehydrating a bio-1-alkanol having a carbon chain of about 5 to about 20 carbon atoms to a bio-1-alkene with a regioselectivity of at least about 80%, more preferably about 92% to about 99%, and most preferably about 95% to about 99%, the bio-1-alkene forming, and then treating the bio-1-alkene with formic acid or acetic acid in the presence of hydrogen peroxide, followed by treating the bio-1-alkene with an alkaline aqueous solution. The bio-1,2-alkanediol can then be separated from the aqueous solution by any suitable technique known in the art for the preparation of dihydroxyalkanes in general, and more specifically 1,2-alkanediol. In a preferred embodiment, a distillation step is included for this purpose.

[0103] Bio-1,2-alkanediols as described above can be used in a variety of compositions, either alone or in combination with other different bio-1,2-alkanediols according to the present invention. Such compositions can incorporate one, two or more different bio-1,2-alkanediols according to the present invention that can function within an antimicrobial system. Such bio-1,2-alkanediols can be used alone as an antimicrobial additive or in an antimicrobial system incorporating other biocompounds (i.e., any suitable naturally derived, preferably authentic natural product tested using mass spectrometry, gas chromatography and / or the above-mentioned ASTM standards), other biocompounds such as bio-organic acids, bio-diols such as 1,3-propylene glycol, bio-1,2-butanediol and 1,2-pentanediol, the bio-diols being extracts of fermentation products of bio-based starting materials and / or other antimicrobial materials, alternative preservatives, traditional preservatives or barrier technology components known in the art or to be developed. An example of a preferred source of biocompounds for use within the scope of the present invention is triglycerides. In yet another example, another chemical group of biocompounds that can be used to prepare alternative preservatives is generally described as terpenoids. These natural terpenoids have 5 to 20 carbon atoms and are easily available through sustainable agricultural practices and can be used in combination with the bio-1,2-alkanediols herein within the scope of the term "biocompound" as used herein.

[0104] When used in a composition, the bio-1,2-alkanediols of the present invention are preferably incorporated in an amount of about 0.1 to about 10 wt %, preferably 0.3 to about 2 wt % of the total composition; the amounts may vary depending on whether they are used alone for antimicrobial effect or used with other components in an antimicrobial system. In the latter case, the bio-1,2-alkanediols are preferably present in the antimicrobial system (where the system will include the bio-1,2-alkanediols herein and / or any other antimicrobial agent, conventional preservative, alternative preservative and / or barrier technology component in the composition) in a ratio of about 99:1 to about 1:99, preferably about 75:25 to about 25:75 of bio-1,2-alkanediol to any other antimicrobial component.

[0105] When used in certain compositions, the compositions themselves are considered "antimicrobial products" for provision to other formulators in various industries. The 1,2-bioalkanediols of the present invention can be initially prepared as antimicrobial products comprising one or more 1,2-bioalkanediol materials made according to the present invention as described above, and incorporating one or more components as described above, wherein such antimicrobial products may also include other biological compounds, known antimicrobial agents, preservatives, alternative preservative materials, or barrier technology materials.

[0106] Examples of known preservatives and alternative preservative materials or compounds used in alternative preservative systems that can be used with the bio-1,2-alkanediols of the present invention include those suitable for various industrial uses in which the present invention may be beneficial. For example, in the cosmetic and personal care industry, the bio-1,2-alkanediols formed according to the present invention can be used alone, in combinations of two or more such materials and / or in combination with other biocompounds and / or with known cosmetic preservatives and alternative preservative materials and / or barrier technology components. Examples of preservatives are listed in the U.S. FDA, which include: (i) traditional preservatives, such as parabens (methyl, ethyl, propyl and butyl), quaternium 15 (also known as "Dowicil"), diazolidinyl urea, imidazolidinyl urea, DMDM ​​hydantoin, 2-bromo-2-nitropropane-1,3-diol (also known as "Bronopol"), sodium hydroxyglycinate, phenoxyethanol, sorbic acid, potassium sorbate, methylisothiazolinone (also known as "MI"), methylchloroisothiazoline (also known as "MCP"), and methylisothiazolinone (also known as "MCP"). The name "CMI" is usually combined with MI as Kaisong CG), sodium benzoate, caprylyl glycol, sodium dehydroacetate and formaldehyde; (ii) non-traditional or alternative preservatives: such as plant extracts, organic acids, alcohols and glycerin, fermentation products, glyceryl caprylate, levulinic acid, p-anisic acid, eucalyptus globulus, glycyrrhiza glabra (licorice) root extract, sage, citrus grandis (organic grapefruit) extract, arnica montana (organic arnica) extract, boraxitrus seed extract, leuconostoc / radish root ferment filtrate, goldenseal (golden seal root) extract extract), citron, limonum (lemon) peel extract, octyl hydroxamic acid; and (iii) so-called "self-preserving" materials, such as ethanol (when present at >15%), butylene glycol (when present at >10%), propylene glycol (when present at >20%); and (iv) other components used in cosmetic alternative or traditional preservative systems, such as MDM hydantoin, sodium hydroxymethylglycinate, benzyl isothiazolinone, benzyl alcohol, dehydroacetic acid, benzoic acid, salicylic acid, iodopropynyl butylcarbamate, chloroxylenol, methyl dibromoglutaronitrile, chlorphenesin, triclosan, benzalkonium chloride, chlorhexidine, polyaminopropyl biguanide, 5-bromo-5-nitro-1,3-dioxane (bronidox), hexamidine di(hydroxyethyl sulfonate), pentylene glycol, ethylhexylglycerol, triclocarban, glyceryl caprylate, O-cymen-5-ol, chlorophenyl ether and glyceryl monolaurate, as well as traditional petrochemically derived 1,2-alkanediols such as 1,2-hexanediol and 1,2-octanediol.

[0107] Other countries have similar lists, with slight variations depending on the nature and type of preservatives, alternative preservatives or preservative systems or barrier technology additives that may be used in those countries. However, the bio-1,2-alkanediols of the present invention may also be used in such other materials. In each of the above systems and compositions, the preferred bio-olefin for use in the present invention is bio-octenes, and the at least one first bio-1,2-alkanediol is bio-1,2-octanediol.

[0108] Examples of compositions that may benefit from an antimicrobial system incorporating one or more bio-1,2-alkanediols formed according to the above process and / or components as described above include personal care compositions, such as hair care, oral care, skin care, or cosmetic ingredients; household product compositions, such as fabric care or cleaning products; industrial compositions; and pharmaceutical, vitamin, nutraceutical compositions, or other health care compositions, any of which may benefit from an antimicrobial system, component, or antimicrobial product derived from authentic, natural, bio-based materials.

[0109] Preferably, bio-1,2-alkanediol is incorporated into the cosmetic or personal care composition (by wet weight or by total weight) to constitute from about 0.001 wt% to about 25 wt% of the composition, more preferably from about 0.01 wt% to about 10 wt% of the composition. This amount can vary depending on whether other barrier technology components or other preservatives are also used in the composition.

[0110] In methods of providing an antimicrobial effect to a composition, such bio-1,2-alkanediols are used alone, in combination of two or more different bio-1,2-alkanediols, and / or in an antimicrobial system incorporating the bio-1,2-alkanediol alone or with other bio compounds and / or other preservatives, alternative preservatives or barrier technology components, wherein the composition may be any of the various types of compositions as above. Whether incorporated into a personal care, household, industrial, pharmaceutical, vitamin, nutraceutical or other health care composition, preferably the bio-1,2-alkanediol herein provides an antimicrobial effect and efficacy to the composition into which the bio-1,2-alkanediol has been incorporated. Such antimicrobial effect can be confirmed using a variety of suitable antimicrobial effectiveness tests (AETs). Such tests include, for example, compendial testing during formulation development and stability testing in parenteral drug products intended as multi-dose products. Appropriate test procedures and acceptance criteria are described in the United States Pharmacopoeia, AET, European Pharmacopoeia (Efficacy of Antimicrobial Preservation), and Japanese Pharmacopoeia (Preservation Effectiveness Tests). Other appropriate challenge tests may be used. FDA also recommends appropriate challenge tests.

[0111] One group of antimicrobial agents (some of which are in the above groups) are other alcohols, preferably at least one other alcohol, preferably at least one other diol, and most preferably one or more other vicinal diols which may be petrochemically derived, although preferably these materials are used with diluents or in smaller amounts to provide some antimicrobial effect, but not so much as to reduce the impact of the natural, bio-based 1,2-alkanediols of the present invention. The term "vicinal diol" refers to a material in which the hydroxyl groups are bonded to atoms adjacent to each other in the molecule, i.e., in which two atoms each bearing a hydroxyl group are bonded to each other. Examples of vicinal diol compounds suitable for use in the present invention include, but are not limited to, ethylene glycol and propylene glycol. Such materials are used as humectants and solvents in the personal care, cosmetic and pharmaceutical fields, and have some moderate antimicrobial activity as described in U.S. Publication No. 2007-0207105-A1.

[0112] Preferred vicinal diols for use with bio-1,2-alkanediols in the personal care and pharmaceutical compositions described herein are medium chain length linear vicinal diols that exhibit some antimicrobial activity, including petrochemically derived 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, and 1,2-decanediol. Other vicinal diols that can be used in the compositions herein include molecules derived from glycerol. Glycerol can be reacted with other molecules at its 1- or 3-position, leaving two adjacent hydroxyl groups. For example, glyceryl monoethers, such as ethylhexylglycerol [3-(2-ethylhexyloxy)propane-1,2-diol], can be used as SC50 is commercially available from Schulke & Mayr and is a useful, conventional, liquid vicinal diol with antimicrobial properties. Glycerol monoesters such as glyceryl monolaurate, glyceryl monocaproate or glyceryl monocaprylate (the latter commercially available from Inolex Chemical Company, Philadelphia, Pennsylvania, USA) are also useful antimicrobial vicinal diols. For the preservation of cosmetic, toiletries and pharmaceutical products, vicinal diols are known to be effective against bacteria and yeasts, but weak against fungi, and there are only limited natural options to date, none of which, to the applicant's knowledge, are biologically derived natural 1,2-alkanediols of 5 to 20 carbon atoms.

[0113] The compositions herein preferably do not include, or include only small amounts of, any preservative materials such as parabens, or other preservative materials known to be considered harmful to the user.

[0114] Such personal care and pharmaceutical compositions may optionally further include a solubilizer in an amount of about 1 wt % to about 70 wt % of the combination of the solubilizing material and the bio-1,2-alkanediol (or if used with other preservative components, based on the weight of the entire antimicrobial system and solubilizing material). Suitable solubilizers include ortho- and other conventional diols.

[0115] Also used with bio-1,2-alkanediol in any antimicrobial system are hydroxamic acids and the like, which can be used in various industries. Suitable hydroxamic acids include alkyl hydroxamic acids and bio-alkyl hydroxamic acids, which include at least one alkyl group with a chain length of about 2 to about 22 carbon atoms, which can be branched or linear structures, substituted or unsubstituted, and saturated or unsaturated as above. Preferred alkyl hydroxamic acids contain alkyl groups with a chain length of about 6 to about 12 carbon atoms, and most preferably straight chains of this length. The most preferred alkyl hydroxamic acids are octyl hydroxamic acid with a linear terminal chain of 8 carbon atoms and caprohydroxamic acid with a linear chain of 10 carbon atoms. Such alkyl hydroxamic acids can be used alone or in combination, and are used in the amount of the optional solubilizer described above.

[0116] Formulations and pharmaceutical compositions prepared for personal care use, depending on the end use (topical or oral), may include any other colorants, fragrances, active ingredients or other additives commonly used in the art and / or to be developed for use in personal care and pharmaceutical formulations, wherein the additives will vary depending on the dosage form in which the preferred bio-1,2-alkanediol or antimicrobial product or system containing bio-1,2-alkanediol is used, for example, in topical toners, skin cleansers, night creams, skin creams, shaving creams, skin lotions or other cosmetic formulations; cosmetics , such as foundation, liquid and powder makeup, mascara, lipstick, blush, highlighter, eyeliner, etc.; or other personal care and / or pharmaceutical compositions, such as sunscreen, lip balm, fragrance, massage oil, shampoo, conditioner, conditioning shampoo, hair styling gel, hair repair, hair tonic, hair fixative, hair mousse, bath and shower gel, liquid soap, moisturizing spray, cosmetics, formula powder, bath additives, ophthalmic preparations, soap foam and shower gel, sanitary wipes, hand sanitizer, medicine (tablet or liquid), wet napkins and wipes, etc. Based on the present disclosure, it should be understood that a variety of personal care and pharmaceutical compositions can benefit from the properties of the bio-1,2-alkanediol of the present invention, wherein as used herein, a pharmaceutical composition is a composition having at least one active pharmaceutical ingredient (API).

[0117] If the personal care and pharmaceutical formulations are liquid based (e.g., gels, hydrogels, detergents, shampoos, liquid medicines, etc.), it is also preferred to include water as part of the liquid matrix. Depending on the desired final formulation, the formulations and compositions may also include other additives such as, but not limited to, at least one humectant, at least one emulsifier and / or thickener, chelating agents, gelling agents, amino acids, emollients, various solvents, free radicals and initiators, UVA sunscreens and / or UVB blockers, antioxidants, other preservatives, waxes, polymers and copolymers, inorganic and organic pigments and / or one or more fragrances, adjuvants, colorants, herbs, natural extracts, essential oils, pharmaceutical preparations, other APIs, and other additives commonly used in such formulations.

[0118] The personal care and pharmaceutical compositions using the bio-1,2-alkanediols herein can be detergent-based, oil-in-water emulsions, water-in-oil emulsions, water-in-silicone emulsions, silicon-in-water emulsions, gels, solids, liquids, cream-based, oil-based, water / alcohol or ethanol solution-based, dispersions, suspensions or syrups, microemulsions, or liposome-based formulations.

[0119] In water-based formulations, except for solids and thicker gels, etc., it is generally preferred to incorporate from about 20 wt % to about 95 wt % (on a wet basis) of water. Various additives other than the water and preferred antimicrobial systems noted herein will make up the remainder of various personal care and pharmaceutical compositions. Preferably, each additive is present in an amount of up to about 75 wt %, more preferably up to about 40 wt % of the entire formulation, and the total amount of such additives is preferably no greater than about 50 wt %.

[0120] In household products, antimicrobial agents are also useful additives.Household product compositions can include household cleaners and fabric care compositions.Cleansing compositions (whether solid or solution) can be incorporated into detergents, which are active ingredients (bleach, vinegar, ammonia, citric acid, etc.) for cleaning.For liquid detergents, aqueous solutions known in the art or to be developed, such as quaternary ammonium compounds, bleach, vinegar, or alkaline or acidic detergents can be used.Commercially available quaternary ammonium-based cleaning products include various antimicrobial general-purpose cleaners, etc., which are intended to and are very suitable for sterilization or disinfection effects, however, such compositions will still be incorporated into antimicrobial agents and other preservatives to extend shelf life and prevent foreign matter growth.Therefore, such compositions also benefit from the use of natural bio-1,2-alkanediol herein.

[0121] For more natural cleaning solutions, such as citric acid-based agents or other green cleaners (environmentally friendly), consumers will be interested in additional additives that are also natural and, in this case, derived from biological sources. Therefore, such compositions benefit from the natural bio-based 1,2-alkanediol herein and antimicrobial systems and products incorporating bio-1,2-alkanediol. Such natural cleaning compositions, as well as standard cleaning compositions as above, may also incorporate various optional additives in varying amounts as follows. Citric acid-based cleaning products may include cleaners based on lemons, oranges, or grapefruits. Other suitable components may include grape seed oil; vegetable oils mixed with one or more mild peroxides; surfactants, etc.; and one or more pigment or colorant additives to provide a visual reminder when the cleaning agent is present; conventional or alternative preservative compounds, antimicrobial agents, bactericides or fungicides (each of which may be used with the bio-1,2-alkanediol of the present invention or used in combination with it in an antimicrobial system or product), thixotropic agents and rheology modifiers, pH adjusting additives or buffers, and fragrance additives for providing a clean scent (pine, lemon, orange, floral, etc.). In addition, if desired, other agents for foaming, color change or effervescence (bubbling) may be provided to exhibit cleaning behavior. Solid cleaning agents may incorporate similar additives, but may be compressed, incorporated or formed by depositing the cleaning material on a substrate (sponge, scrubber, mop head, etc.), and various inactive agents (hardeners, gelling agents, mineral powders, etc.) for holding the solid cleaning material together. Other additives for household cleaning compositions may include known or yet to be developed pH buffers, fragrance encapsulation or carriers, fluorescers, hydrotropes, detergents, polyelectrolytes, enzymes, fluorescent brighteners, antioxidants, ultraviolet absorbing compounds, propylene glycol, dipropylene glycol, opacifiers, pearlescent agents and combinations of these and other cleaning product additives.

[0122] Fabric care compositions may include any active fabric cleaning component and various softening components known in the art or to be developed. Such compositions may include ingredients for fabric cleaning or washing, fabric softening or softening, fabric dyeing, water quality improvers and / or fabric care compositions such as stain removers or stain treatments. Such ingredients include, but are not limited to, defoamers, anti-deposition agents, perfumes and their carriers or encapsulants, traditional or conventional diols (although such diols may be omitted if bio-1,2-alkanediols are useful at the same or enhanced or increased dosage of existing diols), colorants such as pigments or dyes, and co-softeners. Other additives for the fabric care composition may include, but are not limited to, other conventional preservatives, antimicrobial agents, bactericides and / or fungicides (each of which may be used alone or in the antimicrobial products or systems described herein), pH adjusters or buffers, fluorescent agents, hydrotropes, soil release agents, polyelectrolytes, enzymes, fluorescent brighteners, anti-shrinkage agents, anti-wrinkle agents, anti-spot agents, antioxidants, ultraviolet absorbing compounds, corrosion inhibitors, drapeimparting agents, antistatic agents, ironing aids, anti-odor compounds, perfume capsules, cottonseed oil, tea tree oil, aloe extract, propylene glycol, dipropylene glycol, opacifiers, pearlescent agents, and combinations of these components.

[0123] The antimicrobial bio-1,2-alkanediols herein can also be used to treat finished textiles and / or treat fibers or yarns from which textiles are made to achieve the desired benefits. Textiles can include woven and nonwoven textiles, such as felt and cotton and other bark cloth, or blends and combinations thereof. Textile fibers (whether or not they are in the form of finished textiles, yarns or fibers) can be any textile fibers known or developed in the art, and include synthetic fibers, "natural" fibers, such as animal-derived fibers or cellulose / plant-derived fibers, and blends or combinations of any of these.

[0124] Animal-derived fibers may include and be derived from hair or fur of an animal. Examples are, but are not limited to, lamb or sheep wool, alpaca, angora, azlon, byssus, camel, cashmere, chiengora, chatgora, llama, mohair, arctic musk ox, angora, silk, vicuna, yak, pashmina, and combinations thereof. Cellulosic or plant derived fibers may include, but are not limited to, fibers derived from flax (linen), cotton, ramie, jute, kenaf, beach hibiscus, rose hemp, urena, hemp (e.g., Crotalaria juncea, Cannabis sativa, Apocynum cannabinum), hoop vine, sisal, henna, yucca, abaca, chloris, New Zealand flax, cotton, coconut fiber, milkweed, kapok, embroidery thread, hookweed, bamboo, inner bark, fiqui leaf fiber, banana, modal, lyocell, bromeliad, raffia leaf fiber, rayon, soy protein, acetate, and combinations thereof. Synthetic fibers may include any known or yet to be developed, such as, but not limited to, acrylic, Modified acrylic acid, Nylon, polyester, lycra, spandex, rayon, and combinations thereof.

[0125] Fabric treatment compositions can be applied to textiles or fibers. The compositions can be applied as wet compositions or dry compositions and used during a wash cycle with water or a drying cycle. Such fabric treatment materials can be used to soften and / or soften textiles or fibers; reduce and / or prevent wrinkles, impart fragrance to textiles or fibers; reduce ironing time, increase softness, etc.

[0126] The present invention also encompasses the use of 1,2-bioalkanediol materials formed according to the present invention as materials that enhance the antimicrobial efficiency of existing antimicrobial agents, preservatives, alternative preservative materials, and / or barrier technologies.

[0127] By enhanced antimicrobial efficacy, it is meant that when combined with 1,2-bioalkanediol, the antimicrobial efficacy of existing antimicrobial agents and / or preservatives (including alternative preservative materials or barrier technologies) achieves an improvement over insubstantial antimicrobial efficacy, i.e., an improvement of at least about 5%, preferably at least about 10%, and more preferably at least about 20% or more, while providing a natural enhancing material. The enhanced efficacy and antimicrobial efficacy in the formulation are evaluated by measuring performance using a preservative efficacy test ("PET") or challenge test. Preservatives and antimicrobials used in cosmetic, toiletries, and pharmaceutical products must enable the product to successfully pass a microbial testing program, i.e., a "challenge test" established by government regulations and trade organizations. Challenge tests are performed by adding a known amount of microorganisms to the product and measuring the increase or decrease in the microbial population over time. Organisms include Gram-positive bacteria, Gram-negative bacteria, yeasts, and molds. The Cosmetic, Toiletries, and Fragrance Association (CTFA) has defined challenge tests that are widely accepted as standards in the cosmetic, toiletries, and pharmaceutical industries. The test requires a 99% reduction in bacterial count within 7 days and a 90% reduction in yeast and fungi (mold) count within 7 days. In order to pass the challenge test, the product must contain an appropriate amount and type of preservative compound that can have antimicrobial efficacy against a broad spectrum of microorganisms in a short period of time.

[0128] In addition to the aforementioned provision of antimicrobial efficacy, if 1,2-bioalkanediol is used as an enhancing material to improve the effectiveness of existing antimicrobial agents, etc., as described above, it is preferably incorporated in an amount of about 0.1 to about 10 wt %, and preferably 5.0 to about 3.0 wt % of the total composition; and in a ratio of about 99.999:0.001 to about 0.001:99.999, preferably about 99.9:0.1 to about 0.1:99.9, of the total amount of existing antimicrobial, preservative, alternative preservative and / or barrier technology components already present in the composition.

[0129] The invention will now be described with reference to the following non-limiting examples:

[0130] Example

[0131] Bio-1-octanol is formed from the hydrogenation of bio-octanoic acid (a suitable source of which may be derived from coconut, palm or any other renewable source or process that can produce octanoic acid). The bio-1-octanol is regioselectively dehydrated by feeding the bio-1-octanol at elevated temperature into a fixed bed reactor containing a catalyst according to the present invention.

[0132] Gas chromatography (GC) is an important method for characterizing both petroleum and natural renewable derivatives. Products such as octenes were characterized using a Thermo Science Trace 1310 gas chromatograph, which uses a FID detector and Chromeleon software (version 7.2.4.8525). For the dehydration reaction products, GC used a Restek MXT-5 column (30 m long, 0.5 μm film, 0.53 ID), helium carrier gas (3.0 mL / min), CT split injection 45 mL / min (5.0 mL / min purge flow), injector 250°C, detector 300°C, oven 70°C for 8 min, then increased to 300°C (15°C / min), and finally maintained for 6.67 min. For GC analysis of the alkanediol product, a Restek MXT-WAX column (30 m length, 0.5 μm film, 0.53 ID) was used, helium carrier gas (5.0 mL / min), CT split injection 10 mL / min (5.0 mL / min purge flow), injector 220°C, detector 250°C, oven 70°C for 0.25 min, then increased to 250°C (10°C / min), and finally held for 6.67 min.

[0133] Example 1

[0134] The γ-alumina powder was treated with an aqueous solution of calcium acetate using the incipient wetness technique and calcined in air at 440°C for 12 h to obtain a catalyst containing 1.50% calcium (based on CaO).

[0135] Example 2

[0136] The γ-alumina powder was treated with an aqueous solution of calcium acetate using the incipient wetness technique and calcined in air at 500°C for 12 h to obtain a catalyst containing 1.50% calcium (based on CaO).

[0137] Example 3

[0138] The catalyst prepared in Example 1 and Example 2 was loaded into a separate 75mL (Sigma Aldrich article number Z173592) reactor, each of which was wrapped with heating tape and covered with glass fiber insulation. The temperature was controlled by fixing a thermocouple to the shell of the reactor, which was input for a temperature controller. Bio-1-octanol was fed to a reactor maintained at 315°C using an HPLC pump. The bio-1-octanol feed rate was adjusted in a manner to obtain a conversion greater than 95%, but less than 100%. After 1h of continuous operation, samples were collected and analyzed for analysis of the chemical conversion of bio-1-octanol and the regioselectivity of bio-1-octenes. The results are shown below:

[0139] Table 2

[0140]

[0141] Example 4

[0142] Gamma-alumina in the form of 1 / 16" extrudates Cut to have an aspect ratio in the range of 2 to 4. The extrudates were modified with an aqueous solution of calcium acetate. The solution was 0.55 wt% relative to the weight of the alumina and the calcium acetate concentration was a level to deliver 1.50% CaO (after calcination). The catalyst was calcined in air at 440°C for 12 h.

[0143] Example 5

[0144] 48 g of the catalyst prepared in Example 4 was loaded into a 75 mL (Sigma Aldrich Product No. Z173592) reactor, wrapped with heating tape, and covered with fiberglass insulation. The temperature was controlled by fixing a thermocouple to the shell of the reactor, and this input was used for the temperature controller. Bio-1-octanol entered the reactor maintained at 315°C at 0.2 mL / min. After TOS exceeded 1400 h, including routine shutdowns and startups, the performance of the catalyst 1) chemical conversion of bio-1-octanol, 2) product selectivity, 3) and regioselectivity of bio-1-octene no longer changed. The GC chromatogram of the crude product collected from the reactor is shown in Figure 3 The octene selectivity was 96% and the chemical yield of bio-1-octene was 94%.

[0145] Example 6

[0146] The product in Example 5 was subjected to simple distillation at atmospheric pressure. The obtained product was analyzed by GC, and the chromatogram showed Figure 4 The distilled product is 99.9% bio-octene, containing 96.7% bio-1-octene.

[0147] Example 7

[0148] The product in Example 6 was converted to bio-1,2-octanediol by treatment with formic acid and peroxide, followed by alkaline hydrolysis, and finally purified by fractional distillation. The GC chromatogram is shown in Figure 5 The bio-1,2-octanediol obtained in this example had a chemical purity of 98.7% by GC analysis. A typical GC chromatogram of petroleum-1,2-octanediol currently used in commercial cosmetic applications is shown in Figure 6 middle.

[0149] Example 8

[0150] Stable isotope analyses were performed for petroleum-based products and those products prepared from natural and renewable feedstocks prepared in Examples 6 and 7. The values ​​are as follows:

[0151] Table 3

[0152] Compound <![CDATA[δ 13 C]]> <![CDATA[δ 2 H]]> Bio-1-octanol 32.3 -273 1-Octanol (petroleum base) 30.3 -87 Bio-1-octene 32.0 -288 1-Octene (petroleum based) 31.8 Not tested Bio-1,2-Octanediol 32.2 -245 1,2-Octanediol (petroleum based) 31.5 -50

[0153] Example 9

[0154] The bio-1,2-octanediol prepared in Example 7 was subjected to testing currently used to identify petroleum, non-renewable, non-nature equivalents. The bio-1,2-octanediol prepared in Example 7 was found to meet all batch analytical testing requirements:

[0155] Table 4

[0156] analyze Natural 1,2-octanediol Petroleum 1,2-octanediol illustrate odor conform to conform to mild Color, Lovibond (yellow) 0.1 0.1 ≤1.5 Color, Lovibond (red) 0.0 0.0 ≤0.3 precipitation conform to conform to No discoloration Color, APHA 142 8 1 ≤100 Color, APHA 142-01 8 1 ≤30 Infrared spectroscopy conform to conform to Matching criteria Hydroxyl value Mg KOH / g 761 740 740-770 Moisture %w / w 0 0 ≤2 Appearance conform to conform to Clear liquid above 35℃ Determination, % 98.7 99.5 ≥98.0 % of 1,2-octane oxide 0.1 0.1 Report results Color 999-03 conform to conform to Matching criteria

[0157] Example 10

[0158] In a comparative example, bio-1-octanol was fed into a 75 mL reactor filled with a catalyst prepared as follows: gamma-alumina powder was modified with sodium hydroxide solution (5 wt-% NaOH) to produce a second catalyst, the second catalyst was dried in an oven, and then treated with diethoxydiphenylsilane (1 wt-% based on alumina) dissolved in ethanol. The solvent was removed, the catalyst was washed with ethanol, and dried in an oven to produce a third catalyst. The third catalyst was calcined at 400°C for 12 h. The catalyst was loaded into a 75 mL reactor, heated to a target temperature of 325°C and the bio-1-octanol feed rate was adjusted to optimize the conversion and regioselectivity.

[0159] Embodiment 11

[0160] Petroleum-1-hexanol was fed into a 75 mL reactor filled with the catalyst prepared in Example 4. The catalyst used in this example has a TOS of greater than 1400 h and is used for the dehydration of bio-1-octanol to bio-1-octene. For this series of dehydration reaction examples, the temperature was varied from 330°C to 370°C, and the feed rate was adjusted to achieve 1% to 2% hexanol passing through the reactor. The results of the hexanol dehydration are shown below:

[0161] Table 5

[0162]

[0163] In Example 11C, where the reactor was maintained at 370°C, a new peak appeared in the GC chromatogram with an area % of 3.6; thus, indicating a lower chemical yield of 1-hexene and the formation of another product.

[0164] Example 12

[0165] After 1400 h of TOS for bio-1-octanol dehydration, some catalyst was removed on the inlet side of the tubular reactor. Figure 7 In the figure, the used catalyst is pictured together with the catalyst with a TOS of 0 h. The used catalyst showed only a slight discoloration and, as herein, no loss in chemical conversion or regioselectivity.

[0166] It will be appreciated by those skilled in the art that changes may be made to the above embodiments without departing from the broad inventive concept of the present invention. Therefore, it should be understood that the present invention is not limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A process for synthesizing bio-1,2-alkanediol, comprising: Providing bio-olefins having a carbon chain of 6 to 14 carbon atoms and produced at a conversion of at least 95% and a bio-1-olefin regioselectivity of 95% to 99%, the bio-olefins being produced by dehydration of bio-1-ols in a reactor having a calcium-promoter treated gamma-alumina catalyst calcined at a temperature of 420 to 480° C., wherein the catalyst is not silylated; and converting the bio-olefins into bio-1,2-alkanediols having 6 to 14 carbon atoms, wherein the process produces at least 72% to 99% bio-1,2-alkanediol.

2. The process according to claim 1, wherein The bio-1-ol, the bio-olefin and the bio-1,2-alkanediol all have 6 to 10 carbon atoms.

3. The process according to claim 2, wherein: The bio-1-ol, the bio-olefin and the bio-1,2-alkanediol all have 6 to 8 carbon atoms.

4. The process according to claim 1, wherein: The bio-1-ol is 1-octanol, the bio-olefin is bio-octene and the bio-1,2-alkanediol is bio-1,2-octanediol.

5. The process according to claim 1, wherein: The reactor is a fixed bed reactor.

6. The process according to claim 5, wherein: The fixed bed reactor is a fluidized fixed bed reactor.

7. The process according to claim 1, wherein: The process produces at least 92% to 99% of the bio-1,2-alkanediol.

8. The process according to any one of claims 1 to 7, wherein The calcium promoter is used in an amount of 0.01 wt % to 4 wt % based on the weight of the CaO measured after calcination.

9. The process according to claim 8, wherein The calcium promoter is used in an amount of 1 wt % to 2 wt % based on the weight of the CaO measured after calcination.

10. The process according to any one of claims 1 to 7 and 9, wherein The temperature during calcination is 440°C to 460°C.

11. The process according to claim 1, wherein: Calcination is carried out in an oven.

12. The process of claim 1, wherein: The calcination is performed in an atmosphere of air or an inert gas.

13. The process of claim 1, wherein: Prior to converting the bio-olefin into the bio-1,2-alkanediol, the bio-olefin is subjected to a distillation step to refine the bio-olefin.

14. The process of claim 1, further comprising distilling the bio-1,2-alkanediol.

15. The process of claim 1, wherein: The dehydration is carried out in water under a purge gas.

16. The process of claim 1, wherein: The bio-olefin is converted into the bio-1,2-alkanediol by reacting the bio-olefin and a peroxide in the presence of at least one of formic acid or acetic acid to form a bio-1,2-epoxyalkane having an epoxy ring, and contacting the 1,2-epoxyalkane with water and sodium hydroxide to form the bio-1,2-alkanediol.

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