CN101128539B - Candle and candle wax containing metathesis and metathesis-like products - Google Patents

Abstract

A wax comprises a metathesis product and/or a product that resembles, at least in part, a product which may be formed from a metathesis reaction. The wax may be used to form articles, for example, candles (container candles, votive candles, and/or a pillar candles), crayons, fire logs, or tarts. The wax commonly includes other components in addition to the metathesis product.

Description

The material and the transposition shape product that contain candle and candle wax

The cross reference of related application

The application requires the right of priority of US60/642600 that submitted on January 10th, 2005 and the US60/690122 that submitted on June 13rd, 2005.The content of these patent applications is introduced by reference in its entirety at this.

The right of government

Under the contract number DE-FG36-04GO14016 that USDOE is signed, utilize the support of United States Government to finish the present invention.Government has some rights in the present invention.

Background technology

For a long time, beeswax is usually used in the candle as natural wax.Before for some time, the paraffins parallel with the exploitation oil-refinery industry comes into the market.Produce paraffins by residue (residue leftover) from refining gasoline and motor oil.Paraffins is introduced as mellisic substitute abundant and with low cost, and beeswax becomes more and more expensive and supply is more and more rare.

Now, mineral cerul paraffins is to produce candle and the employed major industry wax of other cerul product.Conventional candle by this wax material production typically sends smog and can produce bad taste when burning.In addition, when candle combustion, can produce particle (" saccharoid ") in a small amount.These particles can influence human health when being inhaled into.The candle that the content of preferred mineral cerul paraffins descends.

Therefore, advantageously have other material, wherein can use described other material to form clean burning basis wax for forming candle.If possible, this material is preferably biodegradable, and is derived from reproducible starting material.Candle basis wax should preference as forming outward appearance and/or sense of touch with pleasant and physical features easily having this material of permission aspect fusing point, hardness and/or the ductility with desired organoleptic properties.

In addition, have number class candle, described candle comprises taper, votive, bearing, container candle etc., and each in them is placed on the employed wax of candle with its own unique requirement.For example, wherein wax and candle wick remain on container, and typically the container candle in glass, metal or the analogue requires lower fusing point, specific combustion characteristic, the molten bath of broad for example, and should adhere on the wall of container requiredly.The outward appearance that in a single day molten wax rehardens and should preferably be consistent.

The trial of past by plant oil based material preparation candle wax usually has variety of issue.For example, it is reported that plant oil based candle demonstrates one or more shortcoming with respect to paraffins base candle, for example chap, form the stink of gas enclosure and the natural product relevant with soybean material.It is reported, various soya-based waxes also have with optimize flame size, effectively wax and candle wick Performance Match be for homogeneous combustion, maximum combustion time, the product color is integrated and/or the product life-span is relevant performance issue.For aesthetics and functional product surface and the quality that realizes seeking, advantageously developed the new plant oil based wax that overcomes many these defectives as far as possible by the candle human consumer.

Usually prepare candle by melt-processed.For commercial-scale manufacturing purpose, utilize wax powders compression technical elements can have economic advantages at distant view.Yet, be not easy to realize producing excellent candle product by the wax powders compression.By the prescription variable, for example quantity of the cohesion matter of the fusing point of wax, size-grade distribution, wax, the additive such as air freshener and tinting material and consumption etc., and process variable, for example compression time and compression degree influence the compression molding of wax powder.

Now, candle is mainly sold in the U.S. and is used for decoration function and increases family atmosphere.The aspect that becomes more and more important of commercially available candle is the ability of transmission fragrance.Herein, candle manufacturers faces the limitation of present wax system, and this is because of spices and petroleum base wax incompatible causing of chemistry.In preferred production methods (for example, extruding and compression molding), conventional material has limited ability and keeps fragrance.The candle of extruding with the spices excessive loads or the granular candle of compression can cause non-required feature, and for example spices oozes out from candle, thereby cause the outward appearance of oily surface and difference.

Based on the polyol ester material, for example extra wax material of Toenol 1140 exploitation and candle product aspect be continue interesting.Especially, can by extrude and compress technique make aspect the new wax material of candle be continue interesting.

Description of drawings

Fig. 1 is the chemical structure that shows the monomeric embodiment of polyol-ester.

Fig. 2 is the chemical structure that shows the dimeric embodiment of polyol-ester.

Fig. 3 is the chemical structure that shows the trimerical embodiment of polyol-ester.

Summary of the invention

Wax composition of the present invention comprises a kind of or one group of compound of metathesis reaction product and/or simulation metathesis reaction product.Wax composition of the present invention can be suitable for using in forming candle, and/or can provide and can mix the basic Wax composition that forms candle wax with other wax and/or extra composition.This candle typically comprises candle wick and wax.Wax composition can comprise that also can't help metathesis reaction forms the component of (perhaps simulating this product), comprising other wax (for example, mineral wax, natural wax, paraffin and/or hydrogenated vegetable oil).

Wax composition of the present invention generally includes the polyol fatty acid ester component (it is made up of the polyol of part and/or esterification fully) of at least a portion wherein being carried out metathesis reaction, and/or comprises those similar compounds that produce by metathesis reaction.For example, Wax composition can comprise following blend: the hydrogenation metathesis reaction product that (1) is formed by vegetables oil; (2) hydrogenated vegetable oil, for example highly hydrogenated soybean oil.According to some embodiments, the compound that forms by metathesis reaction can comprise the diprotic acid that contains the polyol oligopolymer and/or contain the compound with acid energy (profile) that one or more plant diprotic acid.This diprotic acid subelement is derived from alpha, omega-dibasic acid usually, for example octadecane diacid and the corresponding docosandioic acid with 21 or 24 carbon atoms.Diprotic acid-polyol oligopolymer can contain any amount of unit, but in some embodiments, contain at least a dimer, tripolymer and the tetramer (that is, oligopolymer contains 2,3 or 4 polyol subelements respectively) and can form by containing the oligopolymer that is less than or equal to 8 polyol subelements basically.Diprotic acid can be unsaturated or can be saturated (for example, forming under the situation of oligopolymer in the method by the metathesis product that comprises the unsaturated polyol fatty acid ester of hydrogenation).This polymkeric substance also can comprise by the monoprotic acid subelement of other hydroxyl group sites esterification of polyol subelement.

Composition of the present invention relates to the wax that can use in candle.Some embodiments of wax can have low mineral base paraffin content (for example, be not more than 50% and much lower potentially content).Can be by the ester group material, for example plant oil based wax forms wax, the biodegradable material that described plant oil based wax is normally produced by renewable resources.Because some embodiments of candle can (for example form and can be substantially devoid of mineral base paraffins by the material with low mineral base paraffin content, contain the paraffins that is not more than about 0.5wt%), therefore can emit seldom cigarette ash according to the candle of these embodiments.Low cigarette ash is emitted, biodegradable and make these embodiments become especially eco-friendly product by the combination of renewable starting material production.

Some embodiments of the present composition comprise the triacylglycerol ester raw material of hydrogenation transposition and the blend of highly hydrogenated triacylglycerol ester raw material, its iodine number be not more than usually about 75 and more suitably iodine number be less than or equal to about 50.Suitable example comprises that hydrogenation is that to be not more than the vegetables oil of about 25 transposition and hydrogenation be the blend that iodine number is less than or equal to about 25 vegetables oil to iodine number.This blend can be used as basic Wax composition suitably, when it and another wax material, for example paraffin in conjunction with the time, can be particularly suitable in some candles are used, using.For example, the blend of the vegetables oil of hydrogenation transposition and hydrogenant vegetables oil (iodine number at this blend is not more than under the situation of about 20 (with more suitably being not more than about 10)) can combine with the paraffin (for example fusing point is about 60 ℃-70 ℃) of higher melt, form be suitable for extrude and/or the compression molding candle in the Wax composition that uses.

Wax of the present invention at room temperature can be solid, firm but embrittlement not, somewhat extending usually (malleable) and/or do not have visual free oil.Wax of the present invention especially can be suitable for for example using in container candle, votive candle and the granular candle at the candle that forms many types.In case after the cooling and (for example, after burning in the candle) molten wax that rehardens, wax of the present invention can also provide consistent feature, for example outward appearance.In addition, usually wish wax can with natural color additives blend, so that uniform solid color distribution to be provided.Also usually wish wax can with other additive blend, for example perfume or other spices, and when burning wax/spices blend, can demonstrate good perfume bloom.

Fusing point is about 45 ℃-75 ℃ metathesis product base wax for can be especially favourable using in forming candle.Have higher melt a little, for example about 55 ℃-75 ℃ and this more generally about 60 ℃-70 ℃ class Wax composition can especially wish to use in forming votive and granular candle.Have softer ground a little and/or can be particularly suitable for forming the container candle than the metathesis product base wax of low melting point (for example, about 45 ℃-60 ℃ and more generally about 50 ℃-55 ℃).

In many embodiments of the application, can include the polyol of complete esterification at basic material, for example have on the mixture of triacylglycerol ester etc. of unsaturated fatty acids acidic group and carry out metathesis reaction.The metathesis reaction of basic material that contains the polyol of complete esterification can comprise that also one or more plant the part ester of polyols, for example the DG ester of the monoacylglycerol ester of lipid acid and/or lipid acid.In these and other embodiment, those that resulting composition can contain that the product that forms by metathesis reaction and/or simulation form by metathesis reaction and hydrogenant product subsequently randomly.

In some embodiments, Wax composition can comprise other component, for example mineral wax, free fatty acids, natural wax (for example, vegetable wax or insect wax) and/or other renewable resources sill.In many embodiments, can't help the wax that renewable resources forms preferably only is present in the composition with maximum about 49wt% and common much lower consumption.Can't help a kind of such wax that renewable resources forms is mineral wax.Mineral wax can be a petroleum wax, for example intermediate paraffins wax, crystallite paraffins wax and/or the petroleum wax that is obtained by the crude oil that is refined to other degree.The example of spendable natural wax comprises carnauba wax, gama wax, montanin wax, wool wax and/or beeswax.In some embodiments, Wax composition comprises that being not more than about 25wt% can't help the wax that renewable resources forms.In an embodiment again, Wax composition comprises that being not more than about 10wt% can't help the wax that renewable resources forms.

In some embodiments, can for example hang fine particle or powdered material in soybean oil, Oleum Gossypii semen and/or the plam oil by at vegetables oil, for example silica-gel powder or wheat fiber, thus form candle with the candle wick of less tension force (string).Comprise that in candle wax granulated material can cause two phase materials, and can change the visual appearance of candle.In some embodiments, wax preferably is substantially free of (for example, comprise and be not more than about 0.5wt%) granulated material.Term as used herein " granulated material " is meant when wax and is in molten state following time, is not dissolved in any material in the wax.

Metathesis product base wax also can comprise other additive of trace, with the performance of modified waxes material.The example that can be incorporated into the additive types in the candle of the present invention usually comprises tinting material, spices (for example, spice oil), antioxidant, photostabilizer, wormer and migration inhibitor.

If wax of the present invention is used to produce candle, then can utilize the identical standard candle wick that uses together with other wax (for example, paraffin and/or beeswax).In order to benefit from the environmental safety feature of wax of the present invention fully, it is metal-cored to wish that use does not have, for example the candle wick of lead or zinc core.An example of suitable candle wick material is the cotton core of braiding.Certainly can use the candle wick of any other type.

Can be by comprising that heating metathesis product base wax is to molten state, and fused metathesis product base wax is incorporated into method in the mould that includes layout candle wick within it, form candle of the present invention, fused metathesis product base wax is at the mould internal cooling, so that solidified wax.

Also can form candle of the present invention by compression molding.Usually by being incorporated into Wax particles in the mould and exerting pressure, thereby carry out this method.The gained candle can with compression molding technology in oversteeping (over-dip) in used same type or the dissimilar wax.Certainly, can use many other candle forming techniques.

Also can use metathesis product base wax to form other cerul goods, for example wax crayon, firelog (wax), tart, square billet (billet), sheet material, section bar etc. with dispersive sawdust or agricultural waste.Can plant composition by blended wax and one or more, and extrude or compress said composition, form the cerul goods, thereby prepare this goods.For example, in one embodiment, extrude or molding metathesis product base wax, formation contains fuel source, for example firelog of sawdust.In another embodiment, extrude or molding metathesis product base wax, form and to contain the pigment and the wax crayon of filler randomly.In another embodiment, extrude or molding metathesis product base wax, form the tart that contains spices.

On the other hand, the invention provides a kind of composition of matter, it comprises the metathesis product that is formed by basic material, and described basic material comprises the polyol fatty acid ester with fatty acid composition, and described fatty acid composition comprises at least a unsaturated fatty acids; Wherein said composition comprises the hydrocarbon that is less than or equal to about 200g/mol less than about 1wt% molecular weight.In some embodiments, composition comprises the hydrocarbon that is less than or equal to about 300g/mol less than about 1wt% molecular weight.In some embodiments, composition comprises the hydrocarbon that is less than or equal to about 200g/mol less than about 0.1wt% molecular weight.In other embodiments, composition comprises the hydrocarbon that is less than or equal to about 300g/mol less than about 0.1wt% molecular weight.

Can prepare composition by the method that comprises the steps: the polyol fatty acid ester with fatty acid composition (a) is provided, and described fatty acid composition comprises at least a unsaturated fatty acids; (b) in the presence of metathesis catalyst, make the transposition of polyol fatty acid ester, produce the metathesis product of hydrocarbonaceous, triacylglycerol ester and triacylglycerol ester transposition oligopolymer; (c) distill this metathesis product, remove at least a portion hydrocarbon.Distilation steps can for example be undertaken by the steam stripped composition.

On the other hand, the invention provides a kind of composition of matter, it comprises the metathesis product that is formed by basic material, and described basic material comprises the polyol fatty acid ester with fatty acid composition, and described fatty acid composition comprises at least a unsaturated fatty acids;

Wherein composition comprises more than or equal to the triacylglycerol ester transposition pentamer of about 30wt% and the oligopolymer of Geng Gao sequence.In some embodiments, composition comprises more than or equal to about 40wt% or more than or equal to the triacylglycerol ester transposition pentamer of about 50wt% and the oligopolymer of Geng Gao sequence.Can prepare composition by basic material, described basic material has the fatty acid distribution (profile) that contains less than about 10wt% saturated fatty acid.The representative example of basic material comprises Canola Oil or Toenol 1140.

Embodiment

Some products of those that many candles that exemplify comprise the part that is formed by metathesis product and/or comprise that simulation forms by metathesis reaction.The potential precursor of metathesis reaction is the polyol ester.Common obtainable polyol ester is a vegetables oil.Vegetables oil tends to comprise the polyol of significantly a large amount of complete esterifications that formed by glycerine and lipid acid.

Transposition is catalyzed reaction normally, and comprises by forming and the carbon-carbon double bond that dissociates, and exchanges between the alkylidene unit in the middle of the alkene.Metathesis reaction can take place (being called from transposition) between the molecule of two same types, and/or can take place (being called cross metathesis) between two not similar molecules.

Metathesis reaction can be a reversible, and can reach the wherein thermodynamic equilibrium of alkylene moiety statistical distribution.In addition, the metathesis reaction product can be hydrogenated.

Definition

The vegetables oil of " hydrogenation fully " as used herein is meant that being hydrogenated to iodine number is not more than about 5 vegetables oil." highly hydrogenated vegetables oil " is meant that being hydrogenated to iodine number is not more than about 50 vegetables oil.Although this situation always not, this highly hydrogenated oil typically has fatty acid composition, and described fatty acid composition contains the lipid acid (typically be not more than about 1 or the 18:2 of 2wt%) of considerably less 18:2.Use the raw material of fatty acid of term " hydrogenation " herein, be meant or hydrogenant fatty acid ester based raw material partly or completely.Can use the triacylglycerol ester material of the relative saturation that the precipitation hard butter partly obtains from vegetables oil, rather than use highly hydrogenated vegetables oil.The hard butter part that obtains in such a way mainly is made up of the triacylglycerol ester with saturated and single unsaturated monoprotic acid acyl group.

" polyol ester " as used herein is meant the ester of being produced by polyol.Polyol can comprise greater than two hydroxyls.These polyols can comprise about 10 carbon atoms of 2-, and can comprise 2-6 hydroxyl, but the carbon atom of other quantity and/or hydroxyl are possible equally.Polyol can contain 2-4 hydroxylic moiety.The limiting examples of polyol comprises glycerine, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, 2-ethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, neopentyl glycol, 2,2,4-trimethylammonium-1,3-pentanediol, TriMethylolPropane(TMP) (TMP), sorbyl alcohol and tetramethylolmethane.Neopentyl glycol, TMP, sorbyl alcohol and tetramethylolmethane also can be common polyols.Very common polyol ester as used herein is the ester of glycerine, triacylglycerol ester for example, and perhaps glycerine and one or more are planted the ester of the mixture of other polyol.

Polyol ester component can comprise partial fatty acid ester that one or more plant polyols and/or with the polyol (" fatty acid ester of polyol fully ") of the complete esterification of lipid acid.The example of the fatty acid ester of polyol comprises four esters of triacylglycerol ester, propylene glycol diesters and tetramethylolmethane completely.The example of the part ester of suitable polyol comprises the part ester (for example, the diester of anhydro sorbitol and three esters) of glycerine monofatty ester, lipid acid two glyceryl ester and anhydro sorbitol.In some embodiments, polyol can comprise 2-6 carbon atom and 2-6 hydroxyl.The example of suitable polyol comprises glycerine, TriMethylolPropane(TMP), ethylene glycol, propylene glycol, tetramethylolmethane, anhydro sorbitol and sorbyl alcohol.

Can be by the transesterify of methyl esters of polyol with acid, thus the polyol ester produced.Acid can be lipid acid.Lipid acid can be straight or branched lipid acid.For example, 2 ethyl hexanoic acid is the potential branched chain fatty acid.Lipid acid can be saturated or undersaturated.In addition, lipid acid can be monoprotic acid, diprotic acid or the acyl group functional group of containing some other quantity.

Acyl moiety in polyol ester of the present invention can be derived from any amount of source.For example, it can be the acyl group derived fatty acid by direactive glyceride, two glyceryl ester, Witepsol W-S 55, ester, free fatty acids and/or other source.Non-acyl moiety in the acyl group (" R yl ") can be a straight or branched, and is saturated or unsaturated, and/or contains non-carbon substituting group, comprising oxygen (for example hydroxyl), sulphur and/or nitrogen.Acyl group can comprise the R base, and described R base is the alkyl that alkyl, alkenyl or hydroxyl replace.Many R bases can be straight chain saturation alkane base (" straight chained alkyl ") and/or the single unsaturated alkyl of straight chain (" straight alkenyl ").

In concrete sample, the mixture of isolating acid is called as " acid composition " of this sample herein from the complete hydrolysis of polyol ester.Term " acid composition " is meant appraisable sour residue in various esters.Can easily determine the distribution of acid in the specific mixture of ester by method known to those skilled in the art.

Usually, the oil that extracts from any given plant or animal-origin comprises the mixture of the triacylglycerol ester feature of particular source.The mixture of isolating lipid acid is called " fatty acid composition " of this sample herein from complete hydrolysis triacylglycerol ester and/or other fatty acid ester in concrete sample.The term " fatty acid " composition " be meant appraisable fatty acid residue in various esters.Can pass through method known to those skilled in the art,,, thereby easily determine distribution of fatty acids in the mixture of specific oil or ester then by gas chromatographic analysis for example by gas-chromatography or change into the mixture of fatty acid methyl ester.

Can use method described herein, provide candle by having the fusing point of giving required molding and/or combustion characteristic and/or the triglyceride level sill of solid fats content.The solid fats content of measuring under one or more plant temperature is the measuring of flowing property of triglyceride feedstock.Can pass through dsc (" DSC "), use the method that well known to a person skilled in the art, measure solid fats content (" SFC ").Fat with low solid fats content has lower viscosity, and is promptly mobile greater than the counterpart with high solid lipid content.

Metathesis product and transposition shape product

Metathesis reaction especially can comprise that from the product of metathesis reaction one or more plant appraisable performance and/or compound.The product that is formed by the polyol ester can be included in the interior feature acid of acid distribution (profile), and can contain the oligopolymer of polyol ester.As an example of characterization compound, when significantly a large amount of reactants comprised the monoprotic acid (for example, oleic acid) with carbon-carbon double bond, metathesis product can be included in interior diprotic acid of acid distribution (profile) of composition.The reactant of this example can comprise free monoprotic acid, and can comprise monacid ester.In some embodiments, acid distribution (profile) can comprise the diprotic acid at least about 1wt%.In addition, in these embodiments some, acid distribution (profile) can comprise the diprotic acid at least about 4wt%.Further in these embodiments some, acid distribute (profile) can comprise at least about 15 or the diprotic acid of 20wt%.Diprotic acid can comprise end carboxyl (for example, HO ₂C-(CH ₂) ₁₆-CO ₂H).In some embodiments, straight chain end group C18, C21 and/or C24 diacid can be the diprotic acid of existing main type.In in these embodiments some, acid distribute (profile) can comprise having of lower aq (for example, be not more than whole diprotic acid 10%) less than about 18 carbon atoms and/or greater than the diprotic acid of about 30 carbon atoms.

According to some embodiments, can use olefin hydrocarbon molecules, the use metathesis reaction prolongs or in other cases, changes the length of starting acid molecule (for example, fatty acid molecule).This can cause chain length to increase, and perhaps compares with parent material, and the change of the chain length of acid increases in acid distributes (profile).Therein in vegetables oil some embodiments as the reactant of metathesis reaction, glyceryl ester can have fatty acid distribution (profile), described fatty acid distribution (profile) comprise with in vegetables oil and/or in common reactant, usually find compare the high chain length fatty acids that percentage ratio is high.Therein in vegetables oil some embodiments as the reactant in the metathesis reaction, glyceryl ester can have fatty acid distribution (profile), described fatty acid distribution (profile) comprises and comparing of finding usually that chain length changes lipid acid greatly in vegetables oil and/or in common reactant.

Long chain acid, the variation variant of acid and/or diprotic acid can be unsaturated or saturated.These acid can be straight chains or can be side chains.These acid can hydroxylation or hydroxylation not.These acid can comprise at least about 12 or 18 carbon atoms, and can comprise about 24 or 30 carbon atoms at most.These acid can be the polyols of esterification completely or partially, for example the acyl group of glyceryl ester etc.

If make the ester (using it to refer to ester and/or the spendable precursor of formation ester) of acid moieties carry out metathesis reaction with remarkable a large amount of similar ester with carbon-carbon double bonds, then product can comprise the polymkeric substance (for example, the dimer of the alcohol that connects by diprotic acid, tripolymer, the tetramer etc.) of binary acid alcohol in composition.These polymkeric substance comprise the multiple pure unit (for example polyol) that links together by diprotic acid.In some embodiments, can form ester by polyol.Polyol can be easy to form the polymkeric substance (tripolymer, the tetramer etc.) of higher unit quantity more.Fig. 1 is a chemical structure of describing the monomeric embodiment of polyol ester.Fig. 2 is a chemical structure of describing the dimeric embodiment of polyol ester.Fig. 3 is a chemical structure of describing the trimerical embodiment of polyol ester.

In some embodiments, product comprises at least a dimer, tripolymer and the tetramer (the polyol polymkeric substance that especially contains diprotic acid of diprotic acid alkoxide polymer, for example pass through the unsaturated fatty acids triglyceride level, for example the oligopolymer of the metathesis reaction of soybean oil production).According to many these embodiments, the polyol component comprises that glycerine and dibasic acid component comprise straight chain diprotic acid (for example, straight-chain paraffin and/or normal olefine diprotic acid).In some embodiments, product contains the tetramer of Duoing than dimer or tripolymer and/or the oligopolymer of higher element number, in in these embodiments some, contain oligopolymer than dimer and the more tetramer of trimerical combination and/or higher element number.As herein described in the experimental section, " area % " that the relative quantity of dimer, tripolymer, the tetramer and the unitary oligopolymer of Geng Gao can for example be measured with HPSEC/ELSD operation described herein is the unit sign.In some embodiments, product comprises at least about the tetramer of 30 area % and/or other higher unitary oligopolymer or at least about the tetramer and/or other the higher unitary oligopolymer of 40 area %.In some embodiments, product comprises the tetramer and/or other higher unitary oligopolymer or the tetramer that is not more than about 50 area % and/or other the higher unitary oligopolymer that is not more than about 60 area %.In other embodiments, product comprises the tetramer and/or other the higher unitary oligopolymer that is not more than about 1 area %.In some embodiments, product comprises at least about the dimer of 5 area % or at least about the dimer of 15 area %.In some embodiments, product comprises the dimer that is not more than about 25 area %.In some embodiments, product comprises the dimer that is not more than about 20 area % or is not more than the dimer of about 10 area %.In some embodiments, product comprises the tripolymer at least about 1 area %.In in these embodiments some, product comprises the tripolymer at least about 10 area %.In some embodiments, product comprises the tripolymer that is not more than about 20 area % or is not more than the tripolymer of about 10 area %.According in these embodiments some, product comprises the tripolymer that is not more than 1 area %.

In some embodiments, metathesis product can comprise the polymkeric substance of diprotic acid-polyol.In in these embodiments some, the polymkeric substance of diprotic acid-polyol can comprise cyclic polymer.In some embodiments, the polymkeric substance of diprotic acid-polyol can comprise more than or equal to 4 unitary polymkeric substance more than being less than or equal to 3 unitary polymkeric substance.

In some embodiments, metathesis product can comprise wherein single diprotic acid be bonded to single polyol greater than the molecule on the hydroxyl group sites.

According to the many embodiments that comprise polyol, polyol can comprise glycerine, and/or acid distribution (profile) can comprise lipid acid.According to some embodiments, polyol is made up of glycerine basically.According to some embodiments, acid distribution (profile) is made up of lipid acid and/or diprotic acid basically.In many these embodiments, to (above-described) polyol ester polymer each with reference to and/or restriction may be used on the polyol ester (for example, by vegetables oil deutero-triacylglycerol ester) of complete esterification of glycerine and lipid acid.If reaction is made up of the triacylglycerol ester of lipid acid basically; then the gained metathesis product may comprise that a kind of acid distributes (profile), and this acid distribution (profile) comprises the diprotic acid (promptly tending to by using the diprotic acid type that typically the unsaturated acid type of discovery forms in fatty acid distribution (profile)) of lipid acid.Acid distribution (profile) can comprise that equally also the chain length scope is the monoprotic acid of 12 carbon-at least 30 carbon.

Vegetables oil and other class fat-based materials tend to comprise the different dissimilar in conjunction with what form of the distribution of dissimilar esters-by fatty acid part.Findable exemplary distribution can be different for dissimilar class fat-based materials.In many cases, distribution can not be the representative of statistical distribution.The statistical distribution that certainly, can or can not comprise all kinds ester by the metathesis product of these ester manufacturings.

In some embodiments, metathesis product can reach wherein it and contains point compared with the few unsaturated acid of beginning material.Parent material is that lipid acid polyol sill (for example, from the triacylglycerol of soya-bean oil in) the embodiment, can exist in fatty acid distribution (profile) compared with few unsaturated fatty acids in the beginning material therein.In having some embodiments of fatty acid ester, metathesis product can comprise the lipid acid that is not more than about 2 area %18:3 in fatty acid distribution (profile).In in these embodiments some, metathesis product can comprise the lipid acid that is not more than about 1 area %18:3 in fatty acid distribution (profile).In some embodiments, metathesis product can comprise the lipid acid that is not more than about 30wt%18:2 in fatty acid distribution (profile).In in these embodiments some, metathesis product can comprise the lipid acid that is not more than about 20wt% or is not more than about 10wt%18:2 in fatty acid distribution (profile).In some embodiments, metathesis product can comprise the lipid acid that is not more than about 20wt%18:1 in fatty acid distribution (profile).In in these embodiments some, metathesis product can comprise the lipid acid that is not more than about 10wt%18:1 in fatty acid distribution (profile).

In some embodiments, metathesis product can be the hydrogenation variant of the product of metathesis reaction.In these embodiments, product can comprise less diprotic acid in acid distributes (profile), and the degree of unsaturation of described diprotic acid is greater than saturation ratio.Parent material is in some embodiments of lipid acid polyol based products therein, and product can comprise the lipid acid that is not more than about 1wt%18:3 in its fatty acid distribution (profile).In some embodiments, product can contain the lipid acid that is not more than about 5wt% or is not more than about 1wt%18:2 in its fatty acid distribution (profile).In some embodiments, product can contain the lipid acid that is not more than about 5wt% or is not more than about 1wt%18:1 in its fatty acid distribution (profile).In some embodiments, the fatty acid distribution in the product (profile) comprises at least about 0.2wt% or at least about the lipid acid of 1wt%12:0.In some embodiments, product has and contains the fatty acid distribution (profile) that is not more than about 10wt% or is not more than about 3wt% trans fatty acid.

In some embodiments, the metathesis reaction product of fatty acid-based polyol ester can comprise typically undiscovered fatty acid component in oil base fatty acid distribution (profile).For example, metathesis product can comprise the lipid acid of 15:1 or 15:0.According to some embodiments, fatty acid distribution (profile) comprises the lipid acid with 15 carbon atoms.This can comprise the lipid acid that has 15 carbon at least about 2wt%.According in these embodiments some, fatty acid distribution (profile) can comprise at least about 4wt% or have the lipid acid of 15 carbon at least about 10wt%.As another example, fatty acid distribution (profile) can comprise the lipid acid of 21:1 or 21:0.According to some embodiments, fatty acid distribution (profile) comprises the lipid acid with 21 carbon.

Can there be the hydrocarbon of concentration greatly in (for example when metathesis product is hydrogenated) in some embodiments.In some embodiments, metathesis product comprises the hydrocarbon of the about 50wt% of about 1-.In in these embodiments some other, from metathesis product, remove dealkylation.In these embodiments, metathesis product comprises hydrocarbon that is not more than about 1wt% and the hydrocarbon that is not more than about 0.5wt% potentially.In some embodiments, hydrocarbon is a straight chain hydrocarbon.In some embodiments, hydrocarbon comprises in about 30 carbon atoms of about 6-and in these embodiments some, can comprise at least about 15 and/or is not more than about 24 carbon atoms.In some embodiments, hydrocarbon has the intermediate value or the center weight of about 21 carbon of about 18-.In some embodiments, hydrocarbon has the intermediate value or the center weight of about 20 carbon.In some embodiments, hydrocarbon comprises the hydrocarbon with about 9 hydrocarbon of about 6-at least.

Should be appreciated that metathesis product can and typically comprise the combination of above-mentioned performance really.In addition, be to be understood that transposition shape product can comprise that one or more plant above-mentioned performance or molecular composition, no matter whether it uses metathesis reaction to generate.

Produce the method for metathesis product

According to the embodiment of the inventive method, can separately or plant extra catalyzer and combine any metathesis catalyst known or that develop in the future of use with one or more.The employed metathesis catalyst that exemplifies can comprise based on transition metal, for example the metal carbene catalyzer of ruthenium.It is those commercially available catalyzer of representative that the ruthenium base metathesis catalyst that exemplifies comprises with structure 12 (usually being called the Grubbs catalyzer), 14 and 16, and wherein Ph is a phenyl, and Mes is that mesityl and Cy are cyclohexyl.

The extra potential ruthenium base metathesis catalyst of structure 18-28 representative shown below.It is known in the art using the technology of catalyzer 12-28 and extra relevant metathesis catalyst.

Catalyzer C627, C712, C823 and C827 (wherein Cy is a cyclohexyl) are the extra ruthenium-based catalysts (it is available commercially from Materia) that uses in can metathesis reaction in the method for the invention.

The metathesis catalyst that additionally exemplifies comprises metal carbene complexes and the tungsten carbene complex that is selected from molybdenum, osmium, chromium, rhenium, the tungsten ad lib.Term " complex compound " is meant at least one part or complexing agent coordination or is bonded to atoms metal on it, for example transition metal atoms.In the useful metal carbene complexes, this part is Lewis base typically in alkene, alkynes or olefin metathesis.The representative instance of this part comprises phosphine, halogenide and stable Cabbeen.Some metathesis catalysts can use multiple metal or metal promoters (catalyzer that for example, contains tungsten halide, tetraalkyl tin compound and organo-aluminium compound).

The fixed catalyzer can be used for transposition technology.This fixed catalyzer can use in flow process.The fixed catalyzer can be simplified the purifying of product and reclaim catalyzer, so that recycling catalyst more easily.

The transposition technology of carrying out the manufacture chemical under any condition of one or more required metathesis products can be enough to produce.For example, can select stoichiometric amount, normal atmosphere, solvent, temperature and pressure, to produce required product and to minimize non-required by product.Can in inert atmosphere, carry out transposition technology.Similarly, if alkene or alkynes reagent then can use the inert gasses thinner with the gas form supply.Inert atmosphere or inert gas diluent be rare gas element typically, this means that gas does not interact with metathesis catalyst, so that significantly hinder catalysis.For example, specific rare gas element is selected from helium, neon, argon gas, nitrogen and combination thereof.

Similarly, if use solvent, then can select selected solvent, so that be essentially inertia with respect to metathesis catalyst.For example, the inert solvent comprises aromatic hydrocarbons ad lib basically, for example benzene,toluene,xylene etc.; Halohydrocarbon, for example chlorobenzene and dichlorobenzene; Aliphatic solvents is comprising pentane, hexane, heptane, hexanaphthene etc.; And chloralkane, for example methylene dichloride, chloroform, ethylene dichloride etc.

In some embodiments, part can join in the metathesis reaction mixture.In many embodiments of using part, select the molecule of part as rugged catalyst, therefore can provide the catalyzer upset (turnover) of accelerating.In some cases, part can change reaction selection rate and products distribution.The example of spendable part comprises Lewis base ligands, for example, but is not limited to trialkyl phosphine, for example tricyclohexyl phosphine and tributylphosphine; Triaryl phosphine, for example triphenylphosphine; Alkyl diaryl phosphine, for example diphenylcyclohexyl phosphine; Pyridine, for example 2,6-lutidine, 2; And other Lewis base ligands, for example phosphine oxide and phosphinate (phosphinite).Also can in the transposition process, there be the additive that increases catalyst life.

Use present known catalyzer, the transposition processing temperature may mainly be a speed dependent type variable, wherein selects temperature, provides required product with acceptable production rate.Selected temperature can be greater than-40 ℃ approximately, can be greater than-20 ℃ approximately, and select usually greater than about 0 ℃ or greater than about 20 ℃.Usually, technological temperature can be not more than about 150 ℃ and can be not more than about 120 ℃.Therefore, the temperature range that exemplifies of metathesis reaction can be about 20 ℃-Yue 120 ℃.Can use lower temperature, for example minimize the non-required impurity of generation or help specific response path.

Can under the pressure of any gas alkene, alkynes and/or thinner, carry out transposition technology.Can select total pressure greater than about 30kPa and can be greater than about 100kPa.Usually, total pressure can be not more than about 7000kPa, and can be not more than about 3000kPa.The pressure range that exemplifies of the transposition technology of therefore, carrying out under pressure is the about 3000kPa of about 100kPa-.

Can in technology of the present invention, use the selected metathesis catalyst of any effective level.If catalyzer has big relatively rollover number, then transposition technology precursor, for example the mol ratio of the derivative of unsaturated fatty acids or lipid acid and catalyzer can be the ratio of about at most 10000000-1, but can be not more than about 500000-1.The mol ratio of unsaturated reactant and catalyzer can be greater than about 5-1, and can be greater than about 50-1 or about 100-1.

The mineral wax mixture

Also can form composition by in conjunction with transposition or transposition shape product and mineral wax.Some examples of mineral wax comprise the mineral wax such as montanin wax, peat wax and petroleum wax (vaseline, paraffin, ceresine and ceresin).

Petroleum wax tends to become one of more widely used wax of present candle.Petroleum wax can be the by product of oil refining process, and commercial can be from (Tarrytown, suppliers N.Y.) and so on obtains such as Sonneborn.The quality of the wax that obtains by refinery practice and source and the refining degree that characteristic depends on crude oil.Petroleum wax component in the Wax composition comprises for example paraffin, comprising intermediate paraffin (medium paraffin wax), microcrystalline wax or its binding substances.Yet, also can use the petroleum wax that obtains to other degree by crude oil refining.

Although the definite chemical constitution of these waxes is unknown as yet, because the character of these by products differs from one another in different distil process, so these waxes tend to be made up of all kinds of hydrocarbon.For example, intermediate paraffin is that the straight chain hydrocarbon of about 20-about 40 is formed by the carbon chain length scope usually mainly, and rest part typically comprises isoalkane and naphthenic hydrocarbon.The middle rank melting point of paraffin wax typically is about 50 ℃-Yue 65 ℃.Microcrystalline wax is that side chain and the cyclic hydrocarbon of about 30-about 100 formed by carbon chain length usually, and the fusing point of this wax typically is about 60 ℃-Yue 90 ℃.Can be at Kirk-Othmer, Encyclopedia of Chemical Technology, the third edition, the 24th rolls up, and finds the further instruction of spendable petroleum wax in the 473-476 page or leaf, is introduced into by reference at this.

The wax part of suitable composition typically has the mineral wax part, and it is not more than the 50wt% of the wax part of composition, and the polyol ester composition constitutes the wax part of half at least.The polyol ester moiety can comprise the polyol ester moiety of transesterify and/or the polyol ester moiety of non-transesterify.The polyol ester moiety is preferably based on triglycerin, and also preferably has fatty acid part.Other suitable composition has the mineral wax of maximum about 25wt% and about at most 17wt%.Other suitable composition has and is not more than about 5wt%, but greater than the mineral wax of 0wt%.These compositions preferably have the mineral wax that is not more than about 3wt% and more preferably no more than the mineral wax of about 1wt%.If use mineral wax, then it typically is petroleum wax, for example paraffin.

Other material

Natural wax and synthetic wax can use to form composition in conjunction with transposition or transposition shape product.For example, many biologies (for example insect and animal) and plant form and at room temperature are generally the solid waxy substance.Some examples of all kinds of solid natural biological waxes are beeswax, lanolin, shellac wax, Chinese wax and spermaceti.Some examples of all kinds of natural phant waxes are carnauba wax, gama wax, Japan wax, ouricury wax, rice bran wax, jojoba wax, castor wax, fruit of Grecian Laurel wax, sugar-cane wax and corn wax.Also can be by hydrogenation or the fat-based materials of modification class in other cases, for example vegetables oil so that it at room temperature is essentially solid, thereby forms natural wax.

In addition, can use synthetic wax.For example, can use wax such as polyethylene wax, fischer-tropsch wax, chlorinated naphthalene wax, chemical modification wax, substituted amide wax, alhpa olefin and polymeric alhpa olefin wax.Also can comprising the ester except the triacylglycerol ester, form wax by polyol ester group material.Wax composition of the present invention also can comprise other synthetic materials, for example ethylene vinyl acetate copolymer, ethylene-alpha-olefin multipolymer, siloxanes, PTFE material, free fatty acids and/or fatty acid amide.

One or more kinds in above-mentioned wax and the natural sill can be used in conjunction with metathesis product or transposition shape product, are formed on the suitable material that uses in the candle wax.

Renewable resource material

According to some embodiment preferred, transposition base wax can comprise by renewable resources deutero-material.These materials can comprise natural wax discussed above and can comprise material such as the class fat-based materials of non-waxy.The class fat-based materials that exemplifies can comprise the oil by plant derivation, for example soybean oil, plam oil, sunflower oil and other oil of discussing in this application.These oil can refining, can bleach, can rectifying, can all or part of hydrogenation, and perhaps in other cases can be by its initial state modification.The iodine number of spendable highly hydrogenated oil can be to be not more than about 10.The iodine number of the oil of spendable less hydrogenation (or not hydrogenation) can be at least about 50 or at least about 75.The renewable resources sill also can comprise based on fatty acid part, for example other material of monoacylglycerol ester (for example, Zerol) and DG ester (for example, Stearic diglyceride).

According to some embodiments, wax comprises that 50wt% is by renewable resources deutero-material at least.According in these embodiments some, wax can comprise at least about 70wt% or at least about 85wt% by renewable resources deutero-material.Satisfy these and require the employed material can be fully or be derived from plant and/or insect source basically, and can comprise at least by vegetables oil deutero-signal portion.This material can comprise that wherein metathesis product is derived from renewable resources, for example the metathesis product of vegetables oil.

In some embodiments, can advantageously have with respect to the little sticking wax of other candle wax described herein.Can in some extrusion molding technologies, use this little sticking wax.According in these embodiments some, can use fatty acid-based component, be formed on this wax that uses in the expressing technique, described fatty acid-based component has two relatively large unsaturated or three unsaturated fatty acidss in its fatty acid distribution (profile).For example, except whole hydrogenant soybean metathesis products, wax also can comprise iodine number at least about 80 fatty acid-based component (as, iodine number is the partially hydrogenated oleaginous seed oil of about 80-100).According in these embodiments some, wax can comprise at least about 5wt% (for example, about 5-20wt%) or satisfy the partially hydrogenated oleaginous seed oil of this iodine number regulation at least about 10wt%.Little sticking wax also can comprise the paraffins component, and can have fatty acid-based component requiredly, described fatty acid-based component comprises about 1-10wt% in its fatty acid distribution (profile) polyunsaturated fatty acid (for example, triglyceride level material with fatty acid distribution (profile), described fatty acid distribution (profile) have the lipid acid of about 2-10wt%18:2 and are not more than three unsaturated fatty acidss of about 0.2wt%).

In other embodiments, even more advantageously can have by compressing the wax of (for example, some compression molding technologies) molding.According in these embodiments some, can use fatty acid-based component to form this wax, described fatty acid-based component has two unsaturated or three unsaturated fatty acidss in a small amount in its fatty acid distribution (profile).According to some embodiments, wax comprises basically the fatty acid-based component that does not have (for example, being not more than about 2wt% and preferred unsaturated and/or three unsaturated fatty acidss less than 1wt% two) polyunsaturated fatty acid in its fatty acid distribution (profile).

Instrument (Kit)

Can be used as the part of candle fabrication tool, for example with the ball or the packaged in foil candle wax of wax, described candle fabrication tool typically also comprises the specification sheets of candle wax.The candle fabrication tool typically also comprises the spendable material of formation candle wick.

Performance improves additive

The various painted and flavouring agent of known broad range can use with wax-like materials in the candle manufacturing field.Typically use one or more to plant dyestuff or pigment, the required color and luster of tinting material is provided and uses one or more to plant perfume, spices, essential oil or other perfume oil, provide flavouring agent required smell.Painted and flavouring agent also comprises liquid vehicle usually, and described liquid vehicle changes with employed type of giving the composition of color or fragrance.Preferred liquid organic carrier and the painted and flavouring agent of using, this is compatible because of this carrier and petroleum base wax and relevant organic materials.As a result, this painted and flavouring agent tends to absorb in the wax-like materials easily.Particularly advantageous is when painted and/or flavouring agent are granular particle, to be introduced in the wax-like materials.

Tinting material is an optional ingredients, and is made up of one or more kind pigment and dyestuff usually.Typically be added in an amount of the tinting material of about 0.001-2wt% of wax shape base composition.If use pigment, then typically it for being suspended in liquid medium, the toner of the interior micro mist form of mineral oil for example.Advantageously can use to be suspended in, for example soybean or Semen Maydis oil deutero-vegetables oil, for example pigment of the particulate form in the natural oil by the oleaginous seed source.Pigment typically is the toner of fine grinding, and during with box lunch burning wax, the candle wick of the candle that the final Wax particles that is covered by pigment forms does not stop up.Even the pigment of the toning agent form of fine grinding is generally the colloidal suspension liquid form in carrier.

If use the dyestuff composition, then it may be dissolved in the organic solvent.Disclose in U.S. Patent No. 4614625 and made suitable various pigment and the dyestuff of candle, its disclosure is introduced by reference at this.The preferred carrier that uses with organic dye is an organic solvent, for example low-molecular-weight relatively aromatic solvent, for example toluene and dimethylbenzene.Dyestuff and its carrier form true solution usually.Because dyestuff tends to ionization in solution, so they are more prone to be adsorbed in the granular Wax particles, and the pigmented tinting material tends to remain close to the surface of wax.

Usually design candle, with attracting sense organ, and visual impression.This class candle mixes volatile oil usually in wax shape material of main part.When wax-like materials during fusion, discharges volatile oil in the wax pond of liquefaction in luminous candle.Flavouring agent can be air freshener, wormer or play more materials greater than a kind of function.

The air freshener composition normally contains one or more liquid perfumes of planting volatile organic compoundss, and it can be available from such as IFF, FirmenichInc., TakasagoInc., Belmay, Noville Inc., the flavor suppliers of Quest Co. and Givaudan-Roure Corp. and so on.The most conventional spices material is a volatile essential oil.Spices can be synthetic materials, perhaps natural deutero-oil, for example oil of Bergamot, BitterOrange, Lemon, Mandarin, Caraway, Cedar Leaf, Clove Leaf, Cedar Wood, Geranium, Lavender, Orange, Origanum, Petitgrain, WhiteCedar, Patchouli, Lavandin, Neroli, Rose etc.

For perfumery, the chemical of wide region is known, for example aldehyde, ketone, ester, alcohol, terpenes etc.Spices can be simple relatively on forming, and perhaps can be natural and complex mixture synthetic chemical components.Typical flavor oil can comprise and contain unusual composition, for example timber/earth the base mateiral of santal oil, civet (civet), Herba Pogostemonis wet goods.Flavor oil can have the light fragrance of a flower, for example rose extract or violet extract.Also can prepare flavor oil, so that required fruit smell, for example bitter orange shaddock, lemon or orange to be provided.

For example in United States Patent(USP) Nos. 4314915,4411829 and 4434306, disclose or separately or with the flavor compositions of natural oil bonded synthesis type, at this by with reference to being introduced into.Other artificial eye-liquid spices comprises Geraniol, meraneine, oxymethoxyallylbenzene, isoeugenol, phantol, phanteine, phenylethyl alcohol, methylethylketone, methylionone, isobornyl acetate and analogue.Flavouring agent also can be to contain wormer, for example geranial or therapeutical agent, for example eucalyptus or

The liquid formulations of alcohol (menthol).In case prepare painted and flavouring agent, then in conjunction with required consumption and the employed wax-like materials of formation candle body.For example, painted and/or flavouring agent can be joined in the wax-like materials with granular Wax particles form.When use painted and flavouring agent the two the time, preferably together in conjunction with this reagent, then the gained mixture is joined in the wax usually.Yet, also reagent can be joined in the wax-like materials independently.Add a kind of or these two kinds of reagent in wax-like materials after, by stirring Wax particles and painted and/or flavouring agent together, be coated with this particle.Whipping step is usually by rotation and/or wiping particle and reagent are formed together.Preferably, one or both reagent are uniformly distributed in the particle of wax basically, but optionally, can have distribution patterns more at random fully.When a large amount of relatively granular wax is colored with perfuming, can perhaps realize application step down by using hand assisting of mechanical rotary drum and agitator.

Some additives can be included in the Wax composition of the present invention, move to tendency on the candle outside surface to reduce other component in tinting material, perfume composition and/or the wax.This additive is called as " migration inhibitor " herein.Wax can comprise the migration inhibitor of 0.1-5.0wt%.One compounds that can serve as migration inhibitor is the polymeric alhpa olefin, more particularly, by the alhpa olefin with at least 10 carbon atoms and more generally have about 25 carbon atoms of 10-one or more plant the polymerisate that alhpa olefins form.A suitable example of this polymkeric substance is with trade(brand)name

The alpha-olefin polymers that 103 polymkeric substance are sold (mp168 ℉ (about 76 ℃), available from Baker-Petrolite, Sugarland, TX).Comprise anhydro sorbitol three esters in Wax composition of the present invention, for example Arlacel-65 and/or anhydro sorbitol tripalmitate and relevant anhydro sorbitol three esters that mixture by complete hydrogenant lipid acid forms also can reduce other component in tinting material, perfume composition and/or the wax and move to tendency on the surface of candle.Comprise that the migration inhibitor of any these types also can improve the sinuousness of basic wax material, and in candle formation and the process for cooling process after the incendiary candle flame extinguishes, reduce the probability of its be full of cracks.For example, can advantageously add maximum about 5.0wt% and the migration inhibitor of about 0.1-2.0wt% more generally, for example alpha-olefin polymers is in wax material of the present invention.

By extruding and compressing wax and make the uncompatibility obstruction that the paraffins candle of high spices can be subjected to spices and paraffin.In extruding, under high spices load, wax can not solubilising spices, thereby leave two-phase system in the machine barrel of forcing machine.This will cause that spices leaks out forcing machine, and dyestuff leaves the inner product of candle, and mixes lower spices.Typically, the candle formulation restrictions of extruding is to the spices of about 3wt%.In compression molding, high spices load causes that with paraffin wax is too sticking, so that can't process.After compression cycle, wax tends to adhere on the compression mould, thereby causes the candle defective and to the potential interference of production technique.Typically, the compressed candle formulation restrictions arrives about 1.5% spices.

In some embodiments, compare with the Wax composition that does not comprise metathesis product, Wax composition of the present invention has improved spices carrying capacity.For example for the candle that has strong fragrance when burning is provided, the spices load of increase is required.In the time of in spices is included in Wax composition of the present invention, comprise that typically consumption is the spices of about at most 15wt%.When Wax composition plans to use in the compression molding candle, Wax composition typically comprises the spices more than or equal to about 1.5wt%, the spices of the spices of about 1.5-6wt% or about 3-6wt% for example, when Wax composition is intended for use to extrude in the candle, Wax composition typically comprises the spices more than or equal to about 3wt%, for example the spices of about 3-6wt%.

Candle wax of the present invention also can comprise antioxidant, the antioxidant of the about 10ppm of for example about 1ppm-, and for example tertiary butylated hydroquinone (TBHQ) or Yoshinox BHT (BHT) are with the oxidative stability that improves wax and increase the life-span.Spendable other suitable antioxidant is well known in the art, and comprise ad lib orcin, stearyl hydrazides, 2,6 di tert butyl 4 methyl phenol,

1010 hindered phenol antioxidant are (available from Ciba SpecialtyChemicals (Tarrytown, N.Y.)).Can use sodium ethylene diamine tetracetate and/or other metal chelator, to improve the efficient of this antioxidant.Also can use photostabilizer, for example UV absorption agent (for example, benzophenone and benzotriazole category), free-radical scavengers and hindered amine as light stabilizer (HALS).The example be available commercially from Ciba Specialty Chemicals those (Tarrytown, N.Y.).

Candle wax exemplify performance

The wax that exemplifies comprises metathesis product or transposition shape product.Metathesis product can comprise polyol ester component.Polyol ester component can be full ester (fully esterification), perhaps can be incomplete ester (the potential ester linkage site that has not the polyol that is occupied by acyl group).

The preferred metathesis reaction by precursor mixture, thus metathesis product component in the wax formed.Precursor mixture can comprise polyol ester, free fatty acids, polyol, other ester and/or other component.Especially some most suitable polyol esters comprise the polyol ester of lipid acid.Some typical polyol esters comprise monoacylglycerol ester, DG ester and triacylglycerol ester.Also can use the glyceryl ester of keyed jointing.In addition, glycerine and other glycerine associated molecule (for example, Polyglycerine) can be used as the part of polyol mixture.Precursor mixture preferably includes the polyol base ester mixture that acid composition has a large amount of percentage ratio unsaturated fatty acidss.

That precursor mixture can use is natural, refining and/or winterized stearin/fat, and for example vegetables oil is as the part of precursor mixture.Typical vegetables oil/fat comprises plam oil, palm kernel oil, soybean oil (comprising low linoleic soybean oil), Oleum Cocois, theobroma oil, Semen Maydis oil, peanut oil, cotton seed oil, Canola Oil (comprising high oleic acid Canola Oil), rapeseed oil (comprising the vegetable seed of high erucic acid), sunflower oil (comprising the oleic sunflower oil of height), Viscotrol C, Thistle oil, Toenol 1140, Yatall MA etc.For example, can use the soybean oil under the native state, it can partial hydrogenation, can fractionation, and/or can under some other states, use.Animal-origin, for example the triacylglycerol ester raw material of butter, lard, chicken fat and fish oil also can be used as the precursor mixture of part or all.

The preferred transposition fully of precursor mixture, but can translocate to other degree, maintain simultaneously in these embodiment scopes that exemplify.

Wax can comprise the transposition based products of 1-100wt%.According to some embodiments, wax can contain at least about the metathesis product of 10wt% and can comprise at least about 15wt% or at least about the metathesis product of 25wt%.According to some embodiments, wax can comprise the component except metathesis product that can identify consumption.These waxes can comprise the metathesis product that is not more than about 85wt%, and can comprise sometimes and be not more than about 50wt% or be not more than about 40wt% or be not more than the metathesis product of about 20wt%.

Wax can comprise metathesis product, hydrogenant metathesis product partially or completely for example, and described hydrogenated products can be present in the wax with about 1-100wt%.According to some embodiments, wax can contain at least about 5wt% hydrogenation metathesis product and can comprise at least about 10wt% or at least about the hydrogenation metathesis product of 15wt%.According to some embodiments, wax can comprise the component except the hydrogenation metathesis product that can identify consumption.These waxes can comprise the hydrogenation metathesis product that is not more than about 85wt%, and can comprise sometimes and be not more than about 50wt% or be not more than about 40wt% or be not more than the hydrogenation metathesis product of about 20wt%.

Can form candle by wax according to many embodiments that exemplify.According to some embodiments, candle can be made up of metathesis product basically.According to other embodiment, candle can comprise very small amount of metathesis product.The wax that contains metathesis product or transposition shape product also can comprise the component except transposition or transposition shape part.For example, wax can comprise petroleum base wax component, for example paraffins component.Wax also can comprise the natural wax component, and the example of this wax comprises insect wax and vegetable wax.Wax also can contain non-waxy component, for example free fatty acids, additive etc.Can use additive to increase color or fragrance, obtain anthelmintic wax, improve the compression molding plasticity of wax, the constituents for suppressing migration, and/or exercise any amount of other effective efficiency and/or obtain the wax of any amount effective performance.

Wax composition preferably includes at least about 51wt% by renewable resources deutero-component.More preferably, Wax composition comprises at least about 70wt% by renewable resources deutero-material.In some cases, Wax composition comprises more than or equal to about 90wt% by renewable resources deutero-material.

In some embodiments, candle wax can comprise at least about 10wt% transposition or transposition shape product.In in these embodiments some, candle wax can comprise at least about 15wt% or at least about 20wt% or at least about 30wt% transposition or transposition shape product.In some embodiments, candle wax can be formed (promptly at least about 80wt%) by transposition or transposition shape product basically.

In some embodiments, candle wax can comprise maximum about 50wt% transpositions or transposition shape product.In in these embodiments some, candle wax can comprise transposition or the transposition shape product of maximum about 40wt% or about at most 30wt%.In some embodiments, candle wax can comprise transposition or the transposition shape product that is not more than 20wt%.

In some embodiments, candle wax can comprise the mineral wax of maximum about 50wt%.In in these embodiments some, candle wax can only comprise the mineral wax of maximum about 40wt% or about at most 30wt%.

In some embodiments, candle wax can comprise maximum about 80wt% renewable resources sills (it does not belong to the metathesis product part).In some embodiments, candle wax can comprise maximum about 60wt% or about at most 40wt% renewable resources sill (it does not belong to the metathesis product part).In some embodiments, wax can not comprise renewable resources sill (it does not belong to the metathesis product part) (for example, about at most 15wt%) basically.The renewable resources sill can comprise or basically by class fat-based materials (or binding substances of class fat-based materials), for example vegetables oil and/or hydrogenated vegetable oil are formed.

In some embodiments, candle wax can comprise at least about 20wt% renewable resources sill (it does not belong to the metathesis product part).In some embodiments, candle wax can comprise at least about 30wt% or at least about 50wt% renewable resources sill (it does not belong to the metathesis product part).In some embodiments, candle wax can comprise basically all renewable resources sills (it does not belong to the metathesis product part) (for example, at least about 85wt%).

In some embodiments, candle wax can comprise at least about 1wt% or at least about the free fatty acids of 5wt%.According to some embodiments, candle wax can comprise the free fatty acids that is not more than about 10wt% or is not more than about 5wt%.In other embodiments, candle wax can be substantially free of free fatty acids, and can comprise and be not more than about 1wt% or more desirably, is not more than the free fatty acids of about 0.5wt%.

The preferred fusing point of candle wax is at least about 45 ℃ and be not more than about 75 ℃, but can optionally have or high or low fusing point.According to some embodiments, the fusing point of candle wax can be at least about 55 ℃ and be not more than about 75 ℃ usually, sometimes at least about 56 ℃ and/or be not more than about 60 ℃ or 65 ℃.According to other embodiment, usually the melting range of candle wax is about 50 ℃-Yue 65 ℃ and sometimes at least about 52 ℃ and/or be not more than about 58 ℃.According to other embodiment, the fusing point of candle wax is about 45 ℃-Yue 60 ℃ and sometimes at least about 50 ℃ and/or be not more than about 55 ℃.

The iodine number of candle wax (IV) can be at least about 5 and be not more than about 70.According to some embodiments, the iodine number of candle wax can be at least about 10 or at least about 30.According in these embodiments some, the iodine number of candle wax can be at least about 40.According to some embodiments, the iodine number of candle wax can be maximum about 55 or at most about 20.According in these embodiments some, the iodine number of candle wax can be at most about 15.The iodine number of the candle wax that some exemplify can be about 5-about 20 or about 10-about 15.The iodine number of the candle wax that other exemplifies can be about 30-about 55 or about 40-about 55.

Preferably include any amount of feature according to these candle waxs that exemplify embodiment.For example, when placing common following time of candle heating and cooling condition, the glyceryl part in the wax is preferably kept common β ｀ crystalline structure.

In addition, the polyol wax component in candle wax or the candle wax can comprise the lipid acid that is not more than about 5-15wt%16:0 in its fatty acid distribution (profile).Wax also can contain at its fatty acid distribution (profile) and be not more than the lipid acid that 10wt% has hydroxyl.In addition, wax can contain at its fatty acid distribution (profile) and be not more than 25wt% and have the lipid acid that is not more than 16 carbon atoms or have unary fatty acid greater than 18 carbon atoms.

According to some embodiments, it is little sticking to design wax.According in these embodiments some, wax can comprise in its fatty acid distribution (profile) at least about 1wt% or at least about the lipid acid of 2wt%18:2.In in these embodiments some, the content that still can limit existing 18:2 satisfies minimum threshold value simultaneously.In this subgroup in this embodiment, the fatty acid-based component in the wax can comprise maximum about 15wt% or bigger, the typically lipid acid of about 3-10wt%18:2 in its fatty acid distribution (profile).According in these embodiments some, the content of 18:3 lipid acid can be not more than about 0.5wt% in the fatty acid distribution (profile) of fatty acid-based component.

According to some embodiments, can construct wax and not be clamminess so, still can pass through the compress technique molding simultaneously.According in these embodiments some, the fatty acid-based component in this wax can comprise the lipid acid that is not more than about 5wt%18:2 in its fatty acid distribution (profile).According in these embodiments some, the fatty acid-based component in this wax can comprise the lipid acid that is not more than about 2wt%18:2 in its fatty acid distribution (profile).

According to some embodiments, wax can comprise fatty acid-based material, and can comprise 15:0 lipid acid in the fatty acid distribution (profile) of fatty acid-based material.

According to some embodiments, can design wax and have lower viscosity.According in these embodiments some, wax can comprise in its fatty acid distribution (profile) at least about 1wt% or at least about the lipid acid of 2wt%18:2.In in these embodiments some, still can limit the consumption of existing 18:2, satisfy minimum threshold value simultaneously.In this subgroup of low viscous embodiment, wax can comprise the lipid acid of maximum about 20wt% or about at most 10wt%18:2 in its fatty acid distribution (profile).According in these embodiments some, can in its fatty acid distribution (profile), limit wax to the lipid acid of about 5wt%18:2 at most.

According to some embodiments, can construct wax and not be clamminess so.According in these embodiments some, wax can comprise the lipid acid that is not more than about 5wt%18:2 in its fatty acid distribution (profile).According in these embodiments some, wax can comprise the lipid acid that is not more than about 2wt%18:2 in its fatty acid distribution (profile).

Candle wax can preferably pass through slump test, preferably passes through under at least 120 ℉.

The common fusing point of wax that is suitable as granular candle is at least about 55 ℃ and be not more than about 70 ℃ usually, and fusing point can be at least about 56 ℃ and/or be not more than about 60 ℃ or 65 ℃.The IV of these waxes can about at most 20 or at most about 15 or at most about 5.In some embodiments, the IV scope is about 1-2.Wax can be granular form and can use Wax particles, form granular candle by compression molding.But the granular candle of oversteeping perhaps experiences some other technology, attempts obtaining the candle of uniform outer appearance.

The melting range that is suitable for the wax that in making the votive candle, uses be generally about 50 ℃-Yue 65 ℃ and fusing point can be at least about 52 ℃ and/or be not more than about 58 ℃.The IV of these waxes can be maximum about 20 or at most about 15 or at most about 5.In some embodiments, the IV scope is about 1-2.Can require some votive waxes to pass through slump test.These waxes preferably can pass through slump test under 120 ℉, but if they pass through under the temperature that is low to moderate about 115 ℉ or 117 ℉, then also can accept.

Be suitable for being preferably about 45 ℃-Yue 60 ℃ as the melting range of the wax of container.In some embodiments, its fusing point can be at least about 50 ℃ and/or be not more than about 55 ℃.The IV value of these waxes can be at most about 80 or at most about 55 and can have the IV value at least about 30 or at least about 40.Can be as the wax that is applicable to votive candle wax, these waxes preferably can pass through slump test under 120 ℉, but if they pass through under the temperature that is low to moderate about 115 ℉ or 117 ℉, then also can accept.

Possible situation is to exist for being used as votive and all acceptable waxes of granular wax.In addition, possible situation is to exist for being used as votive and all acceptable waxes of container wax.Although so not general usually, can there be some waxes that are suitable for simultaneously as granular and container wax equally.

The candle that is formed by wax also generally includes candle wick except wax.Can make candle wick by any amount of material, but preferred natural candle wick, for example Bian Zhi cotton core.

Form candle

Can use many different methods, by polyol ester group material produce candle.In a kind of common technology, heating polyol ester group wax is to molten state.If other additive, for example tinting material and/or spices wet goods will be included in the candle prescription, then they can be joined in the fused wax, perhaps before heating, mix with polyol ester group wax.Molten wax then hardens around candle wick.For example, molten wax can be poured in the candle wick layout mould within it.Cool off molten wax then, the wax of sclerosis mold shape.The type that depends on the candle of being produced can make the candle demoulding (unmold), perhaps still under the situation in mould it is used as candle simultaneously.Under the situation that the design candle uses with the form of the demoulding, this candle also can coat the material outer layer of higher melt.

Perhaps, for example by toppling over fused polyol ester group wax in mould and after its sclerosis, taking out formed material from mould, is required shape thereby can make polyol ester group material forming.Can use technology well known by persons skilled in the art, for example use the candle wick machine, for example Kurschner candle wick machine is inserted into candle wick in the wax-like materials of moulding.

Also can use the compression molding technology, be candle with the wax moulding of polyol ester group.It is granular form that this method generally includes wax moulding, then granular wax is incorporated in the compression mould.

Candle wax can manufacture various granular forms, and the general size scope is the efflorescence of length or the about 1/10mm of diameter or pulverizes small pieces, thin slice or other acale wax of Wax particles to length or the about 2cm of diameter.Under the situation that is designed for the compression molding candle, wax shape particle is generally sphere, the granular particle that mean diameter is not more than 1mm.

Can be by fusion triacylglycerol ester group material at first in bucket or similar containers, then through nozzles spray fused wax-like materials in cooling chamber, thereby form granular Wax particles easily.Dispersive liquid will harden when dropping in the chamber by relative colder air imperceptibly, and form granular particle, and for bore hole, described granular particle appears as the sphere near grit size.In case form, granular triacylglycerol ester group material can be deposited in the container, and randomly combines with tinting material and/or flavouring agent.

Can use compress technique,, form candle comprising granular Wax particles with saccharoid.Can use the gravity flowage jar, saccharoid is incorporated in the mould.Mould typically is bronze or teflon mould.Under ambient room temperature (65-85 ℉ usually), apply the physics squeeze between 1000 to 2000 pounds of pressure then.Can be from the top or the bottom exert pressure.The candle that is shaped can be released mould then.The candle that forms by this method may tend to not have uniform exterior sideview.Candle can experience certain heating (being lower than the fusing point of candle) when through forcing machine, described heating is tended to be coated with glaze and removed some uneven outward appearances on the side.Optionally, the candle that forms by this method can be in the liquid wax of heat oversteeping, obtain the candle outside surface of smoother outward appearance.

The equipment and the operation of wax powders compression are disclosed in the publication such as M.Kheidr " Powder Compression of Candles " (International Group Inc., 1990) and so on, at this by with reference to being introduced into.Can be at the die pressure that contains about 1000-4000ps i, the compression time of about 1-20 second and under about 15 ℃-Yue 25 ℃ granular wax temperature condition carries out compression molding.

For the combination that realizes final candle product excellent properties, the size-grade distribution specification of granular Wax composition is important.The size-grade distribution of regulation allows granular Wax composition to have about 0.55-0.65g/cm ³Powder density, and allow the compression molding candle product subsequently, have about 0.8-0.9g/cm ³Density.

In addition, the size-grade distribution specification of granular Wax composition helps the improvement of other key property of final candle product.Undertaken that the particulate height merges and the final candle product is characterised in that required hardness and strength property and high gloss or bright and clean surface of candle modify by the compression molding operation.

Also can form candle, thereby form candle by candle wax according to various embodiments by using extrusion molding wax.In these class methods that form candle, machine promotes wax usually through forming panel.Typically wax is incorporated in the forcing machine with granular form.Can in the expressing technique process, keep the wax of various states, cooling after extruding solidified wax then.In case extrude, typically the wax of the length of Chan Shenging part can cut into required length.

Wax of the present invention also can mix about 0.1-5wt% wax and merge the additive that improves type in carrying out the granular Wax composition of compression molding operation.Suitable wax merges the raising additive and comprises peruscabin, dimethyl phthalate, dimethyl adipate, isobornyl acetate, cellosolve acetate (cellusolveacetate), alpha-glucose pentaacetate, pentaerythrite tetra-acetate, trimethylammonium-s-trioxane and N-Methyl pyrrolidone.Spherulitic composition additive also can have wholesome effect to the combustionproperty of the candle product of compression molding.

When wax being placed in the mould when forming candle, preferred wax has good release property.In order to have " good release property ", preferred wax shrinks fully, so that be separated by between formed candle and mould 1/16 inch.Define the performance-good release property of candle by shrinkage at the wax of given area (it can be by width and length, waits to determine by diameter) inner mold.Is about 4 inches-Yue 7 inches candle for diameter for about 3.5 inches candle and the diameter of about 1.5-, and candle preferably has good release property.Based on the specific area that should be used for determining the demoulding.

Also can pass through extrusion molding molding wax, form candle, thereby form candle by candle wax according to various embodiments.In these class methods that form candle, machine promotes wax usually through forming panel.Before extruding, wax is kept the thickness state, and cooling fast after extruding solidified wax.In case extrude, these long waxes partly are cut into suitable length.

Form the spendable basic technology of candle and also can be used for forming other cerul structure, for example wax crayon, firelog, tart, square billet (billet), sheet material and section bar.Tart is the wax work with high flavour content, and it is used for transmitting spices by indirect heating and fusion.Can be by being similar to the method that candle is made, for example topple over fused and fill a prescription in the mould, extrude and compression molding, thereby make tart.The composition of Tart is similar to those compositions that use in candle.In addition, various other methods that form the cerul goods can be used for forming candle, comprising, but be not limited to curtain coating, injection moulding, cold shaping, vacuum forming, blowing, die casting etc.

Bleaching, distillation and taste removal

Also can bleach polyol ester group wax and taste removal.Can use diatomite to bleach, described diatomite adds by acid activation and under vacuum.This tends to remove the soap class from wax.In addition, can make the taste removal of polyol ester group wax by removing free fatty acids.This can be undertaken by distillation free fatty acids under 450 ℉-500 ℉.Polyol base ester also can carry out other processing and/or purification step.

In some embodiments, the distillation metathesis product is so that remove or reduce hydrocarbon impurity.For example, retortable metathesis product so that remove or reduce the hydrocarbon that molecular weight is less than or equal to about 200g/mol, is perhaps removed or is reduced the hydrocarbon that molecular weight is less than or equal to 300g/mol.In some embodiments, resulting composition comprises the hydrocarbon that is less than or equal to about 1wt%.In other embodiments, resulting composition comprises the hydrocarbon that is less than or equal to about 0.1wt%.In some embodiments, composition comprises the hydrocarbon less than about 0.1wt%.Can prepare composition by the method that comprises the steps: the polyol fatty acid ester with fatty acid composition (a) is provided, and described fatty acid composition comprises at least a unsaturated fatty acids; (b) in the presence of metathesis catalyst, make the transposition of polyol fatty acid ester, produce the metathesis product of hydrocarbonaceous, triacylglycerol ester and triacylglycerol ester transposition oligopolymer; (c) distill this metathesis product, remove at least a portion hydrocarbon.Distilation steps can for example be undertaken by the steam stripped composition.Can be by in container, stirring mixture, typically by stirring, by in the pillar that can contain typical distillation tube (for example at random or structurizing), mixture is contacted with gas stream, perhaps at vaporizer, for example evaporate light ends in the wiped film evaporator, thereby realize distillation.Typically, under reduced pressure and under scope is about 100 ℃-250 ℃ temperature carry out steam stripped.Temperature can be depending on for example employed level of vacuum, wherein higher vacuum lower temperature is provided and provide volatile matter more effectively with separate completely.

List following embodiment, set forth the present invention and auxiliary those skilled in the art's manufacturing and use it.Embodiment in no case plans to limit the scope of the invention.

Embodiment

Unless explanation (for example, under situation about concerning between the oligopolymer of the relative quantity of TAG and metathesis product) is arranged in addition, otherwise all percentage ratios of listing illustrate herein herein with wt%.

Measure polymkeric substance by the efficient size exclusion chromatography (HPSEC/ELSD) that links to each other with vapo(u)rability scattering of light detector

In isolating polymer, use the liquid phase chromatography (LG) of the Waters2795 liquid chromatography that links to each other with vapo(u)rability scattering of light detector (ELSD).The sample of preparation 5mg/ml, and adopt two Plgel, 3 μ m, 100A, 300 * 7.5mm pillar separates.Column temperature is 50 ℃.Need higher temperature, wash-out metathesis product sample from pillar.Mobile phase is that flow velocity is the THF of 1.0ml/min.Volume injected is that 20 μ L and test period are 20 minutes.ELSD is set at 50 ℃, gain factor=6, and nitrogen=3.5bar (50psi).Do not form response factors.List data with the area percent form.

Measure fatty acid composition and oil-contg by direct extraction method (DEM) with the gas-chromatography that links to each other with flame ionic detector (GC/FID)

DEM utilizes alkali soapization (NaOH/MeOH), extraction (organic solvent) and derivatize (BF simultaneously ₃/ MeOH) reaction.Use about 100mg sample.(organic solvent C39TAG) (heptane) joins in the sample, adds saponification reagent then for IS, tritridecanoin will to contain interior mark.Saponification lipoid, and from sample, extract with organic solvent, and all components with esterified fatty acid changes into the salt of free fatty acids (FFA).BF ₃Be catalyzer and have MeOH, form methyl esters.Add saturated sodium-chloride, methyl esters is assigned in the organic layer.By gas-chromatography (GC), on the very large static phases of polarity that links to each other with flame ionic detector (FID) (CP-Sil88,100m * 0.25mm * 0.25 μ m), analyze methyl esters.Temperature program(me) be under the 20 ℃/min from 170 ℃ to 190 ℃ (40 minutes) or under 8 ℃/min to 215 ℃ (25 minutes).Hydrogen be vector gas and in the constant flow rate pattern (under the μ=26cm/s), inlet pressure is 20.8psi.The temperature of syringe and detector is 250 ℃.Splitting ratio is about 100:1.Measure oil ﹠ fat acid content according to Nutritional Labeling and Education Actof1990 (AOAC996.06), and respectively based on the weight percentage of TAG and lipid acid.

Measure hydrocarbon by lipoid distribution (profile)

Use this method, measure the component of broad range by monotechnics.Sample had not both had saponification before deriving, do not have hydrolysis yet, thereby was convenient to distinguish the very large component of boiling point difference, for example distinguished free fatty acids (FFA) and triacylglycerol ester (TAG).The component that is detected covers boiling spread (110 ℃-340 ℃).With the N that contains 1% trimethylammonium chlorosilane and pyridine, two (trimethyl silyl) trifluoroacetamide (BSTFA) the silylation samples (50mg) of O-.Use interior mark (IS) the stearic acid heptadecane ester (HDS) of 10mg.With toluene 1:200 ground dilute sample.(COC) gas-chromatography (GC) (it has the nonpolar pillar static phases (DB-5HT, 15m * 0.25mm * 0.10 μ m) that links to each other with flame ionic detector (FID)) on the logical supercooled post is analyzed trimethyl silane (TMS) ether.Temperature program(me) be under 30 ℃/min from 110 ℃ to 140 ℃ (0.2 minute), under 10 ℃/min to 340 ℃ (10 minutes).Hydrogen is vector gas and under the constant flow rate pattern, and inlet pressure is 6.7psi.The temperature of detector is 370 ℃.Compound for following group: glycerine, fatty acid methyl ester (FAME), fatty-acid ethyl ester (FAEE), FFA, hydrocarbon (HC), monoacylglycerol (MAG), DG (DAG), TAG, sterol, steryl ester (SE), VITAMIN E ACETATE, squalene and tocopherol, exploitation calibration curve.

General procedure 1:

A kind of oil in the presence of ruthenium catalyst from transposition.To be transported to two possible catalyzer then from the oil of transposition and remove (filtration or water/methanol wash) in one of step.Then in the presence of the Ni catalyzer hydrogenation purifying from transposition oil.By removing by filter the Ni catalyzer, obtain final wax product then.

In 50 gallons batch of material, under the estimating speed of 10ml/min, make oily spend the night (～16 hours) that outgas with argon gas or nitrogen.Making the oil degassing tend to the auxiliary metathesis catalyst that prevents decomposes.Heated oil to 70 ℃ then.Add the ruthenium catalyst (C827) of 50ppm.Be reflected at and carried out under the 1atm 2 hours.Do not measure stirring velocity, be enough to cause splashing from the baffle plate a small amount of but stir.Except may forming micro-3-hexene and 1, this mixture should be non-volatile basically under 70 ℃.

Use three (methylol) phosphine (" THMP ") to remove catalyzer, described three (methylol) phosphine is by adding 245g four (methylol) phosphonium chloride (1.03mol, Strem) and 500ml Virahol (IPA) in 2 liters of round-bottomed flasks, make this mixture degassing 20 minutes with nitrogen, in under nitrogen atmosphere, in 30 minutes, slowly add 64g (1.03mol, 90% purity, Aldrich) potassium hydroxide is in the solution of vigorous stirring, add potassium hydroxide afterwards, extra 30 minutes of stirring reaction and preparing.This exothermic heat of reaction, and produce THMP, formaldehyde, Repone K and water.Then by adding 25-100mol equivalent THMP/mol ruthenium catalyst, use THMP, under nitrogen, at 60-70 ℃ of following vigorous stirring 18-24 hour, add the water or the methyl alcohol (～150ml/L reaction mixture) of the degassing, and vigorous stirring 10 minutes and centrifugal this mixture be for being separated, thereby remove catalyzer.Essential heated oil is to remove residual water or methyl alcohol.Water contains IPA in a small amount, formaldehyde and Repone K, and need to purge or clean for circulation.

Then can be by heating from the oil of transposition to 350 ℉, under nitrogen, keep simultaneously, under 350 ℉, add the 0.4wt%Ni catalyzer in oil, under the pressure of 35psi, begin flow hydrogen gas, keeping temperature is about 410 ℉, and in the time of 1 hour detection reaction, observe IV, compare with target compound, thus the hydrogenation metathesis product.2.5kg batch of material can spend about 30-45 minute.After about 2 hours (oil should be hydrogenated fully), supplying nitrogen turns back in the container, and cooling oil.Can filter hydrogenant then from transposition oil, remove catalyzer.

Embodiment 1

Three sample metathesis products (A, C and E) are carried out the metathesis reaction described in the general procedure 1 to different degree.According to these three kinds of metathesis products of general procedure 1 hydrogenation, form the hydrogenation variant (B, D and F) of metathesis product.

By unrefined soybean oil and 100ppm catalyzer C627 is initial, production sample A.Reaction was at room temperature carried out 20 hours, was warming to 40 ℃ through 5 hours then.Use unrefined soybean oil and 50ppm catalyzer C627 production sample C.Reaction was at room temperature carried out 22 hours.Use unrefined soybean oil and 50ppm catalyzer C715 production sample E.Catalyzer C715 is identical with catalyzer C627, and different is that it has bromide part rather than muriate part.Reaction was at room temperature carried out 22 hours.

Polymer analysis shows that each transposition sample and corresponding hydrogenation sample (in bracket) A (B), C (D) are reacted to different terminal points with E (F).Can find out that according to table 1 sample C reaction minimum (most of triacylglycerol esters-TAG-keeps) and sample A reaction be (minimum triacylglycerol ester and the highest oligomer concentrations) at most.HPSEC analysis revealed sample B has 21.2% unreacted triacylglycerol ester, and sample D has 93.3% unreacted triacylglycerol ester and sample F has 80.8% unreacted triacylglycerol ester.Sample A, C and E have the similar HPSEC color atlas of its corresponding hydrogenation sample.Relative quantity is at the area % described in the above experimental section.

Table 1 Wax composition

	A	B	C	D	E	F
							Total oligopolymer	75.6	78.7	6.9	6.7	20.5	19.3
The oligopolymer of the tetramer and Geng Gao	46.1	50.7	ND	ND	0.5	0.4
							Dimer	16.4	16.1	6.5	6.4	16.5	15.9
Tripolymer	13.0	12.0	0.4	0.3	3.5	3.0
							TAG	24.4	21.2	93.1	93.3	79.6	80.8

Table 2 shows the lipid acid of 6 samples and forms.By being designated as the basis with in using, fatty acid methyl ester (FAME) is changed into its triacylglycerol ester Equivalent, so that numerical value is based on weight percentage, thereby measure oil-contg.By FAME being changed into lipid acid (FA) Equivalent and, thereby measure all independent lipid acid based on weight.

Lipid acid in table 2 Wax composition is formed

	A	B	C	D	E	F
							Trans	13.35	1.36	8.02	0.01	11.49	1.65
C18：1(％w/w?FA)	8.06	1.87	20.13	0.11	17.86	2.21
							C18：2(％w/w?FA)	8.81	0.58	41.64	ND	31.78	0.27
C18：3(％w/w?FA)	0.12	0.01	4.01	ND	2.26	0.01
							C18：0(％w/w?FA)	4.03	18.51	4.11	68.12	4.06	50.38
Standard FA (%w/w FA)	17.17	44.69	15.50	83.2	15.59	67.40
							C12：0(％w/w)	0.02	1.17	0.01	0.29	0.02	0.50
C15：0(％w/w)	0.04	10.70	0.03	2.73	0.03	4.55

Embodiment 2

To be similar to the mode of sample A, be initial by purified blanching soya beans oil, production sample G and I.Use 100ppm catalyzer C627, at room temperature carried out production sample G 18 hours.Use 100ppm catalyzer C627, at room temperature carried out 19 hours, thus production sample I.Hydrogenation sample G and I form sample H and J respectively.Some analytical resultss have below been comprised, but when this material of hydrogenation, there is the material that to identify potentially, the described material that can not identify occurs at the identical point place that the conjugated linolic acid occurs in analytic process, and/or the total oligopolymer (the especially oligopolymer of the tetramer and Geng Gao sequence) that causes obvious amount occurs, and changes in hydrogenation process as them.

Table 3 and 4 shows the analysis of lipid acid and the oligopolymer of sample G-J.The relative quantity of oligopolymer is at the area % described in the above experimental section.

The lipid acid of table 3 Wax composition is formed

	G	H	I	J
					Trans (%w/w FA)	12.26	1.30	19.66	2.46
C18：1(％w/w?FA)	6.41	1.57	13.63	2.16
					C18：2(％w/w?FA)	7.12	16.66	9.77	17.86
CLA retention time * * (%w/w FA)	0.35	16.58	2.80	17.14
					C18：3(％w/w?FA)	0.31	0.03	0.34	0.04
C16：0(％w/w?FA)	10.69	12.56	10.23	11.42
					C18：0(％w/w?FA)	4.24	16.62	4.29	16.80
Standard FA (%w/w FA)	18.62	45.74	18.22	44.23
					C12：0(％w/w)	0.02	1.37	0.02	1.22
C15：0(％w/w)	0.01	11.85	0.02	11.28

Table 4 Wax composition

	G	H	I	J
					Total oligopolymer	83.7	70.2	82.1	71.4
The oligopolymer of the tetramer and Geng Gao	67.7	46.6	55.1	48.7
					Dimer	12.7	12.2	14.1	12.5
Tripolymer	13.3	11.4	12.9	10.2
					TAG	16.3	29.7	17.9	28.2

Embodiment 3

Table 5 shows the comparison of hydrocarbon (HC), polymkeric substance and the C6-C15 fatty acid content of hydrogenation metathesis product B, D, F, H and J.The relative quantity of polymkeric substance (opposite with TAG) is at the area % described in the above experimental section.

The performance of table 5 Wax composition

	B	D	F	H	J
						HC	9.10	1.78	3.58	1.69	6.10
C6-C15FA	22.86	5.97	10.03	23.34	2.93
						Polymkeric substance	78.7	6.70	19.3	70.2	71.4

Embodiment 4

The metathesis product that use is formed by soybean oil, formation can be suitable for as candle, the wax of especially granular and votive candle.With described those the similar conditions of the metathesis product B of embodiment 2 under, form metathesis product, different is that purified blanching soya beans oil is as initial product.Metathesis product has and the similar feature of the product B of embodiment 2.This metathesis product and one or more kinds are hydrogenated to the IV value are not more than about 5 soybean oil (" FH-SBO "), are hydrogenated to the IV value and are about 65 soybean oil, be hydrogenated to IV value and be about 90 soybean oil, paraffin and/or free stearic acid combination.Can heat the component that constitutes gained wax and also stir, with each component of thorough blend to 170 ℉ (about 77 ℃).Table 6 shows some compositions of the wax that exemplifies.

Granular/votive the prescription of table 6 compression

	FH-SBO	Molten wax J	Molten wax H	The 65IV soybean oil	The 90IV soybean oil	Paraffin (p) or beeswax (b)	Free stearic acid	Fusing point (℉)	Iodine number
										Blend 5-1	45	30	0	25	0	0	0	136	17
Blend 5-2	45	35	0	20	0	0	0	136.7	12.4

Blend 5-3	40	35	0	20	0	0	5	136.2	12.2
										Blend 5-4	35	35	0	20	0	0	10	135.4	11.9
Blend 5-5	27	0	21	12	0	40p	0	143.2	9.2
										Blend 5-6	31	0	21	8	0	40p	0	145.3	6.8
Blend 5-7	27	0	21	0	12	40p	0	143.2	12.6
										Blend 5-8	21	0	21	0	18	40p	0	144.1	17.8
Blend 5-9	21	0	21	0	15	40p	3	139.5	15.2
										Blend 5-10	29	0	21	0	10	40p	0	145.1	10.8
Blend 5-11	24.2	0	17.5	0	8.3	50p	0	145.5	9.4
										Blend 5-12	33.8	0	24.5	0	11.7	30p	0	143.3	12.3
Blend 5-13	34	0	21	0	5	40p	0	ND	ND
										Blend 5-14	40	20*	0	0	0	40p	0	145	<5
Blend 5-15	65	35*	0	0	0	0	0	139.4	<5
										Blend 5-16	40	20*	0	0	0	40b	0	143
Blend 5-17	53.6	26.4*	0	0	0	20b	0	138

*-the complete hydrogenant transposition soybean oil of using difference with similar characteristics to criticize forms these blends.

In any one prescription, the 90IV soybean oil in the prescription shown in the table 6 (with in following table 7) can be substituted by the soybean oil of purified bleaching and taste removal (RBD).

Embodiment 5

Use the metathesis product of embodiment 1, formation can be suitable at candle, especially the wax that uses in container or the votive candle.Be hydrogenated to the IV value in conjunction with this metathesis product and one or more kinds and be about 0 soya-bean oil, be hydrogenated to IV value and be about 65 soya-bean oil, be hydrogenated to the IV value and be about 90 soya-bean oil, and free fatty acids.Can heat each component that constitutes gained wax and also stir, with each component of thorough blend to 170 ℉ (about 77 ℃).Table 7 shows some examples of some waxes that exemplify.

Table 7 container prescription

	OIV soya-bean oil	Transposition wax H	Transposition wax J	65IV soya-bean oil	90IV soya-bean oil	Free stearic acid	Fusing point (℉)	Iodine number
									Blend 6-1	0	100		0	0	0	127.4	1.8
Blend 6-2	13.5	10		76.5	0	0	127.3	47.9
									Blend 6-3	14.8	1		84.2	0	0	132.1	52.5
Blend 6-4	14.7	2		83.3	0	0	131.4	51.9
									Blend 6-5	14.4	3		81.6	0	0	131.1	50.9
Blend 6-6	14.2	5		80.8	0	0	130.6	50.5
									Blend 6-7	8.5	10		76.5	0	5	127.5	47.5
Blend 6-8	0		85	0	10	5	125.3	10.5
									Blend 6-9	27.5		35	0	32.5	5	126.9	30.6
Blend 6-10	12		10	68	10	0	128.2	51.6

Embodiment 6

Transposition and the hydrogenation of carrying out the fried oil in exhausted restaurant as described below.The used oil frying oil placed in the 600ml Parr reactor and with minimum 4 hours of argon purge.(Materia Inc.) and heat this reaction mixture to 70 ℃, and kept temperature of reaction 3 hours to add ruthenium catalyst.(Johnson Matthey Catalysts) joins in the reactor with nickel catalyzator, and with nitrogen purging 3 times.Below show the relative quantity of employed catalyzer.Use the hydrogen purge reactor then 2 times.Make reactor be pressurized to 50psi with hydrogen, and be heated to 190 ℃.When reaching required temperature of reaction, increase hydrogen pressure to 100psi.Holding temperature and pressure 2 hours.

The fried oily 100%w/w in exhausted restaurant

C827 ruthenium catalyst 0.05%w/w

Pricat9920 nickel catalyzator 0.02%w/w

Last in reaction, relief pressure, and cooling reactor is to＜80 ℃, and oil is filtered by fine filter paper, remove catalyzer.After cool to room temperature, oil is white waxy solid.Compare with the iodine number of initial used oil frying oil 107, the iodine number of final oil is 50.

Embodiment 7

Producing under the employed standard conditions of metathesis product (referring to general procedure 1) by soybean oil, adopt the metathesis catalyst load of 500ppm, many oil are carried out metathesis reaction.Then according to the operation described in the embodiment 8-13, hydrogenation gained metathesis product.Some features of hydrogenant metathesis product have been summarized in the following table 8.

Table 8 hydrogenant transposition oil

Starting oil	Iodine number	Fusing point (℃)
			Canola Oil	14	50.3
Soybean oil * *	2	53
			Toenol 1140	5.2	49.4
Plam oil	0.65	53.4
			Butter	0.46	56.3
Fish oil	2.5	42.8
			Viscotrol C	28	48.5
The used oil frying oil	50

*-transposition wax H

Embodiment 8

Transposition Viscotrol C (299.5g) and nickel catalyzator (1.26g, Pricat9920, Unichema International) are placed in the 600ml stainless steel Parr pressure reactor.Sealing Parr reactor, and, it is heated to 190 ℃ then with nitrogen purging 5 times, be pressurized to 100psi at least with hydrogen to container pressure.Under 700rpm, stirred content 3.0 hours down then, keep the hydrogen pressure of 100psi simultaneously at 190 ℃.Cool off Parr afterwards to about 120 ℃, open, and by fine filter paper vacuum filtration winterized stearin, to remove catalyzer.The iodine number of titration final product (IV) is determined degree of hydrogenation.The iodine number of products therefrom is 14, and fusing point is 50.3 ℃ and is the canescence waxy solid.

Embodiment 9

(5.66g, Pricat9920), and under 190 ℃, hydrogenation as described above is 2.0 hours under the hydrogen of 100psi with nickel catalyzator for the Viscotrol C (300.2g) of mixing transposition.The iodine number of products therefrom is 28, and fusing point is 48.5 ℃ and is grey/black waxy solid.

Embodiment 10

Two steps were carried out the hydrogenation of transposition fish oil.(1.07g, Pricat9920) blended transposition fish oil (261.3g) under 190 ℃, carry out the first step hydrogenation 6.0 hours under the hydrogen of 100psi with nickel catalyzator in employing.Products therefrom still is a liquid.Use the oil with extra nickel catalyzator (11.02g) blended equal in quality, under 200 ℃, under the hydrogen of 100psi, this mixture is carried out other 4 hours of the second step hydrogenation.At second product of step after the hydrogenation is soft linen waxy solid, its IV value be 2.5 and fusing point be 42.8 ℃.

Embodiment 11

Divide two portions to carry out the hydrogenation of transposition Toenol 1140.(1.27g, Pricat9920) blended transposition Toenol 1140 (299.6g) under 190 ℃, carry out the first step hydrogenation 3.0 hours under the hydrogen of 100psi with nickel catalyzator in employing.Products therefrom still is a liquid.Use is added with the 218.6g of extra nickel catalyzator (11.00g) from the first step hydrogenant oil, under 190 ℃, under the hydrogen of 100psi this mixture is carried out other 2.0 hours of the second step hydrogenation.At second product of step after the hydrogenation is linen solid, its IV value be 5.2 and fusing point be 49.4 ℃.

Embodiment 12

(1.49g Pricat9920), and under 200 ℃, stirred 2.0 hours under the hydrogen of 500psi the plam oil (302.5g) of mixing transposition with nickel catalyzator.The iodine number of products therefrom is 0.65, and fusing point is 53.4 ℃, and is almost the waxy solid of paper white.

Embodiment 13

(1.54g Pricat9920), and under 200 ℃, stirred 2.0 hours under the hydrogen of 500psi the butter (300.7g) of mixing transposition with nickel catalyzator.The iodine number of products therefrom is 0.46, and fusing point is 56.3 ℃, and is the waxy solid of paper white.

Embodiment 14

With the RBD soybean oil (～780kg) be incorporated in the container that 2600L has stirring.Spend the night with argon purge container and soybean oil then.Heat the temperature of soybean oil to 70 ℃ then, and 39g (50ppm) C827 ruthenium metathesis catalyst is joined in the soybean oil, cause metathesis reaction.Adopt the slight head of argon gas to press (～2psig), operation has the container of stirring.Metathesis reaction was carried out two hours.Followed by in container, keeping transposition oil extra 4-5 hour.Followed by, be used for the hydrogenant preparation method, transposition oil is transferred in the maintenance jar of stirring.Then the transposition oil content is become 4 batch of materials about equally for hydrogenation, so as to hold obtainable 300L have stirring, pressure nominal container.For all batch of materials, use the load of 0.4wt%Ni hydrogenation catalyst (Pricat9925 is available from Johnson Matthey).Summarized the reaction conditions of four kinds of hydrogenation batch of materials in the table 9.

Table 9

Batch of material	Batch sizes	Temperature	Hydrogen pressure	Reaction times
					1	194kg	210℃	50psig	4.0 hour
2	193kg	175℃	90psig	4.0 hour
					3	193kg	185℃	90psig	2.3 hour
4	180kg	185℃	90psig	2.7 hour

Before filtering, in the 2600L stirred pot in conjunction with four kinds of hydrogenant products.Keep bonded hydrogenation transposition oil down at 70 ℃.Mix citric acid (0.1wt%), bleaching clay (2.0wt%) and filtration adjuvant (0.1wt%) and oil, flow through frame filter (4 * 2`` frame) afterwards.Because in passing through for the first time, therefore the fracture of one of filter paper requires to pass through for the second time.After filtering, reclaim 675kg hydrogenant transposition soybean oil.

Embodiment 15

18300 pounds of RBD soybean oil (Cargill) are transferred in the reaction vessel of nitrogen purging from jar.In about 4 gallons soybean oil, make 415g (for final reaction mixture, the 50ppm catalyzer) C827 metathesis catalyst slurryization independently.The gained slurry joined in the soybean oil in the reaction vessel that under 70 ℃ temperature, keeps.In reaction vessel, keep about 3 hours time period of reaction mixture then.The sample of GC analyze reaction mixture shows that about 30 minutes after adding metathesis catalyst locate, and reaction mixture is reached balance.

Next, 27.5 pounds of (12.5kg) hydrogenation catalysts (PRICAT9925 is available from Johnson Matthey) are incorporated in this container.After adding catalyzer, be incorporated in the head space in the container followed by hydrogen.During this period, reacting by heating mixture to 120 ℃.When temperature reaches 120 ℃, increase the pressure of the interior hydrogen of head space to 50psig.Utilize the temperature to 185 ℃ of the heat rising reaction mixture of thermopositive reaction.Continue to introduce hydrogen extra 3 hours.The final IV value of the soybean oil of transposition is less than 1.

In identical reaction vessel, introduce the steaming out of stable state, by steam stripped, remove the bigger component of volatility.Cooling vessel to 120 ℃ in stripping process.Under 120 ℃, by circulation products through having about 25 pounds of diatomite filtration auxiliary agents (available from EaglePicherFiltration, Reno, frame filter (the Sparkler of precoated layer " CELATOMFW-14 " of NV), Conroe TX), filters products therefrom.The content of final Ru is the Ru less than 0.07ppm.

Embodiment 16

15900 pounds of RBD soybean oil (Cargill) are loaded in the reaction vessel.Stir soybean oil, and under the speed of 50SCFH, use nitrogen purging 2.5 hours.In about 3 gallons soybean oil, make 361g (for final reaction mixture, the 50ppm catalyzer) C827 metathesis catalyst slurryization independently.The gained slurry is joined in the soybean oil in reaction vessel.Followed by after adding catalyzer, the head space in the evacuated vessel, and in 1 hour time period, use nitrogen purging 3 times.During this period, reacting by heating mixture to 71 ℃.Kept reaction mixture about 3 hours then in reaction vessel, during this period, temperature is elevated to 76 ℃.GC analyze reaction mixture sample shows that about 30 minutes reaction mixtures after adding metathesis catalyst reach balance.

Next, 35.0 pounds of (15.9kg) hydrogenation catalysts (PRICAT9925 is available from Johnson Matthey) are incorporated in this container.After adding catalyzer followed by evacuated vessel in head space, and in 1 hour time period with nitrogen purging total 3 times.During this period, reacting by heating mixture to 130 ℃.When temperature reaches 130 ℃, hydrogen is incorporated in the container.Hydrogenation in 30 minutes makes reaction mixture reach 180 ℃ temperature, and stops about 75 minutes time period of flow hydrogen gas.Afterwards, begin extra 3 hours of the introducing of hydrogen again, during this period, temperature range is 172 ℃ to 194 ℃.The temperature of cooling gained hydrogenant transposition soybean oil to 84 ℃, and the excessive hydrogen of finding time.Before filtering, oil is maintained at about under the 5-8psig about 9.5 hours.

(Sparker, Conroe TX), filter products therefrom through the frame filter of precoated layer with about 25 pounds of diatomite filtration auxiliary agents (available from EaglePicher Filtration, Reno, " CELATOMFW-14 " of NV) by circulation products.Product cycles through strainer and amounts to about 13 hours.In filtration procedure, twice minute opened filter be for cleaning, and regulate with about 25 pounds filtration adjuvant.In filtration procedure, the temperature of product is for being less than or equal to about 90 ℃.The content of final Ru is less than 0.1ppm.

Embodiment 17

Each transposition oil for described in the embodiment 7 uses about 20g material.Oil is placed in the glass round-bottomed flask, and at room temperature apply vacuum (less than about 1Torr).In case the termination bubbling then according to following temperature curve, applies heat to oil:

(1) in 15 minutes from room temperature heated oil to 150 ℃.Kept oil 15 minutes down at 150 ℃.

(2) in 15 minutes from 150 ℃ of heated oil to 200 ℃.Kept oil 15 minutes down at 200 ℃.

(3) in 15 minutes from 200 ℃ of heated oil to 250 ℃.Kept oil 15 minutes down at 250 ℃.

In distillation, the volatile matter that condensation is collected, and collect and analyze for GC.Remain on all the other materials (that is residue) of not distilling out in the flask for gpc analysis.The distillation result has been shown in the table 10.

Table 10: distillation result

Employed transposition oil (g)

Collected volatile matter quality (g)

Residue quality (g)

Volatile matter wt%

Residue wt%

Canola Oil (21.4)	3.2	17.1	15	81
					Viscotrol C (20.7)	4.2	15.8	20	76
Fish oil (20.7)	2.8	17.4	14	84
					Toenol 1140 (21.3)	2.8	18.1	13	85
Plam oil (20.9)	1.7	18.9	8	90
					Soybean oil (21.6)	2.9	18.3	13	85
Sunflower oil (21.5)	3.2	17.9	15	83
					High oleic sunflower oil (21.4)	3.9	17.1	18	80
Butter (21.1)	1.7	18.9	8	90

The lipid acid that some vegetables oil have been shown in the table 11 form and table 12 in be shown forming of hydrogenation metathesis product (after the stripping) made by this oil.Shown in these data, the variation that saturated fatty acid content is relatively little causes visibly different distribution of polymer (profile) in the hydrogenation metathesis product.For example, soybean oil typically contains the saturates (main lauric acid and stearic lipid acid) of the 16wt% that has an appointment.Just as shown in table 12, the soybean oil of hydrogenation and transposition has the higher oligomers content (being pentamer and Geng Gao) of 18wt%.By contrast, Canola Oil and Toenol 1140 have the saturates of 7wt% and 10wt% respectively, and produce the hydrogenation metathesis product with 43wt% and 41wt% higher oligomers (being pentamer and Geng Gao).

Shown in these data, the variation that saturates content is relatively little in the starting oil causes more than the double amount of higher oligomers in hydrogenation transposition oil.Toenol 1140 and Canola Oil prove another unforeseeable result, are to exist many unsaturatess and single unsaturates to seem that distribution to oligopolymer has influence seldom.

The typical IV value of table 11 lipid acid composition and reagent oil

Sample	Saturates %	Monounsaturated fatty acids %	Polyunsaturated fatty acid %	Hydroxy fatty acid %	Iodine number
						Soybean oil	16％	24％	61％	0％	133
Canola Oil	7％	65％	28％	0％	113
						Viscotrol C				95％
Toenol 1140	10％	20％	69％	0％	186
						Plam oil	51％	39％	10％	0％	50
Butter	54％	43％	3％	0％	44

Table 12 gel permeation chromatography is analyzed steam stripped hydrogenation and transposition oil

Sample

～280 g/mol (lipid acid and hydrocarbon)

～340 g/mol (direactive glyceride)

～600 g/mol (two glyceryl ester)

～800 g/mol (triacylglycerol ester and monomer)

～1200g/mol (dimer)

～2000 g/mol (tripolymer)

～2600 g/mol (tetramer)

～3200 g/mol (pentamer)

～3800 g/mol (six aggressiveness)

Soybean oil

2％

0.40％

1％

32％

23％

17％

7％

18％

－

Canola Oil

0.30％

1％

0.80％

17％

14％

12％

6％

43％

5％

Viscotrol C

0.50％

0.50％

1.60％

15％

12％

11％

43％

17％

－

Fish oil

0.10％

0.70％

－

30％

20％

17％

10％

22％

－

Toenol 1140

0.40％

0.30％

0.80％

19％

14％

12％

8％

41％

4％

Plam oil

0.20％

0.60％

3％

45％

27％

15％

4％

4％

－

Butter

－

0.70％

0.60％

44％

25％

17％

5％

8％

－

Embodiment 18

(Cargill RBD oil, 155.8g 0.177mol) 1 hour, remove oxygen with the argon purge soybean oil.Ruthenium metathesis catalyst 827 (1.5mg catalyzer, 10ppm is based on mol/mol) is joined in the soybean oil.Under 70 ℃, stirred the mixture 2 hours, and cool to room temperature.On the methyl alcohol hydrolysis products of the soybean oil of transposition, according to GC assay determination transformation efficiency percentage ratio.

By at catalytic amount sodium methylate (NaOCH ₃, 25wt% in methyl alcohol ,～5 μ l) exist down, under 70 ℃, at methyl alcohol (～0.5ml) sample of internal heating oil (～100 μ l) 30 minutes, preparation methyl alcohol hydrolysis products.The GC condition is as described below: pillar: HP-5 ^TM(30m * 0.25mmID, 0.25 μ m thickness); 100 ℃ 1 minute, 10 ℃/min to 250 ℃, kept 12 minutes; Rt12.6 minute (Uniphat A60), Rt14.2-14.5 minute (Linolenic acid methylester, methyl linoleate and Witconol 2301), Rt14.7 minute (methyl stearate).

According to the GC color atlas, calculate transformation efficiency percentage ratio with 100% form that deducts Uniphat A60, Linolenic acid methylester (cis and trans-isomer(ide)), methyl linoleate (cis and trans-isomer(ide)), Witconol 2301 (cis and trans-isomer(ide)) and methyl stearate sum.Reported transformation efficiency percentage ratio in the table 13.

Table 13: transformation efficiency percentage ratio is as the function catalyst cupport of catalyst cupport

The soybean oil resource	50ppm	40ppm	35ppm	30ppm	20ppm	10ppm
							A	63.61
A	67	65，67	59.67 1	37，52 1
							A	68	68		48	32	15
A	69	69		66	51	28
							A	70	63		38	31	7
A	68	66		11 4	29
							B	60，14 4	38，31 4
C	51	49
							C (citric acid)	68	68		63，68 1，49 6， 49 7，45 6，8，60 7，8	61，62 1	36
C (not having citric acid)	67	66		61	52
							D (citric acid)	71	70		65		23
D (not having citric acid)	71	70，69 9		66，67 9	60	44，40 9(12 9，10)

¹Before metathesis reaction, filter by clay (5wt%). ²After the storage time section in～February, transformation efficiency sharply descends. ³When receiving, oil leaks from its container. ⁴Transformation efficiency sharply descends between the shelf lives. ⁵Oil by good packaging obtains high transformation efficiency. ⁶From testing oil in reserve 26 days (in case opening) for the first time. ⁷From receiving data oils in reserve 28 days (not opening). ⁸Use many new metathesis catalysts for screening. ⁹Liquid storage form as the dilution in DCM adds 827.From testing oil in reserve 42 days (in case opening) for the first time. ¹⁰Add 5ppm827.

The embodiment that exemplifies

An embodiment is that described wax comprises metathesis product as the wax of candle and/or the candle of the content of wax.

Another embodiment is that described wax comprises diprotic acid-polyol oligopolymer as the wax of candle and/or the candle of the content of wax.

Another embodiment is as the wax of candle and/or the candle of the content of wax, and described wax has the acid distribution (profile) that contains at least a diprotic acid.

Another embodiment is as the wax of candle and/or the candle of the content of wax, and described wax has the acid distribution (profile) that contains at least a C9 and C15 acid.This acid distribution (profile) can comprise C9 and C15 acid simultaneously.C9 and/or C15 acid can be straight chains.In addition, C9 or C15 can be saturated, can be single unsaturated, perhaps can comprise some other degree of unsaturation.

Another embodiment is as the wax of candle and/or contains the candle of following ingredients, and is at least a in the hydrogenation metathesis product that is formed by the basic material that contains the polyol fatty acid ester (described polyol fatty acid ester has the fatty acid composition that contains at least one unsaturated fatty acids) and polyol fatty acid ester based raw material, paraffin, lipid acid, carnauba wax and the beeswax.

Another embodiment is as the wax of candle and/or comprises the candle of following ingredients, the hydrogenation metathesis product, polyol fatty acid ester raw material and the paraffin that are formed by the basic material that contains the polyol fatty acid ester (described polyol fatty acid ester has the fatty acid composition that contains at least one unsaturated fatty acids).The fusing point of wax is about 55 ℃-70 ℃.Usually form described hydrogenant metathesis product by vegetables oil basis raw material.

Another embodiment provides candle wax, and described candle wax comprises the hydrogenation metathesis product that is formed by the basic material that contains the polyol fatty acid ester (described polyol fatty acid ester has the fatty acid composition that contains at least one unsaturated fatty acids).Wax also comprises at least a polyol fatty acid ester raw material, paraffin, lipid acid and natural wax, for example carnauba wax and/or beeswax.The fusing point of candle wax usually is about 20 ℃-70 ℃ or about 45 ℃-70 ℃, and wherein designing wax, to be used to form fusing point be about 55 ℃-65 ℃ candle of extruding or pushing.Typically, wax has fatty acid composition, and described fatty acid composition comprises lipid acid and the straight chain end group docosandioic acid of 15:0, for example has the diacid of 18,21 and/or 24 carbon atoms etc.

Candle wax generally includes metathesis product, for example hydrogenation triacylglycerol ester (" TAG ") transposition oligopolymer.Can form metathesis product by containing the basic material that iodine number is at least about 45 vegetables oil.The hydrogenation metathesis product can comprise hydrogenation TAG transposition dimer.In other embodiments, the hydrogenation metathesis product comprises the hydrogenation TAG transposition tetramer.Term as used herein " TAG transposition oligopolymer ", " TAG transposition dimer " and " the TAG transposition tetramer " are meant respectively by one or more plants oligopolymer, dimer and the tetramer that the metathesis reaction of triacylglycerol esters forms.In many cases, the hydrogenant metathesis product also can comprise saturated C15-C24 hydrocarbon, the hydrogenated products that described saturated C15-C24 hydrocarbon is unsaturated C15-C24 hydrocarbon.Wax of the present invention contains the 10-40wt% hydrogenant metathesis product of having an appointment.

In many cases, candle wax can comprise extra wax-like materials.For example, wax can comprise lipid acid, especially saturated fatty acid, for example stearic acid, palmitinic acid or its mixture.Other possible composition can comprise direactive glyceride, for example glyceryl monostearate, monopalmitin or its mixture.Other possible wax material that can be included in suitably in the Wax composition of the present invention comprises petroleum wax, for example paraffin, natural wax, for example carnauba wax and/or beeswax, or the mixture of this wax material.Very commonly, candle wax comprises hydrogenation polyol fatty acid ester raw material, for example complete hydrogenant soybean oil.

Other embodiment relates to wax, and described wax comprises the hydrogenation metathesis product that is formed by the basic material that contains the polyol fatty acid ester (described polyol fatty acid ester has the fatty acid composition that contains at least one unsaturated fatty acids); Polyol fatty acid ester raw material; And paraffin.The fusing point of this wax typically is about 55 ℃-70 ℃.For example, this wax can comprise the hydrogenation metathesis product of about 10-30wt%; The paraffin of about 20-60wt%; Be less than or equal to about 70 triacylglycerol ester raw material with about 20-50wt% iodine number.

Fusing point is that about 45 ℃-75 ℃ metathesis product base wax can especially be advantageously used in the formation candle.Have higher melt a little, for example about 55 ℃-75 ℃ and this more generally about 60 ℃-70 ℃ class Wax composition can be used to form votive and granular candle especially ideally.Have softer ground a little and/or can be particularly suitable for forming the container candle than the metathesis product base wax of low melting point (for example about 45 ℃-60 ℃ and more generally about 50 ℃-55 ℃).

Metathesis product base wax of the present invention usually has the diprotic acid subelement, and described diprotic acid subelement is derived from alpha, omega-dibasic acid, for example octadecane diacid and/or have the corresponding docosandioic acid of 21 or 24 carbon atoms.Again further, in these embodiments some, acid distribution (profile) can comprise about 15-20wt% diprotic acid or more.Diprotic acid can comprise end carboxylic acid group (for example, HO ₂C-(CH ₂) ₁₆-CO ₂H).In some embodiments, straight chain end C18, C21 and/or C24 diacid can be the main types of existing diprotic acid.Diprotic acid and lipid acid, for example the mixture of stearic acid, palmitinic acid and/or 15:0 lipid acid is usually used glycerine esterification, forms to contain TAG, TAG dimer, TAG tripolymer and the tetrameric mixture of TAG.

The candle that is formed by above-mentioned wax typically also comprises candle wick except wax.

Candle (A), it comprises candle wick and contains the wax of metathesis product.The candle of embodiment A, wherein metathesis product comprises polyol ester group metathesis product.The candle of embodiment A, wherein metathesis product comprises fatty oil base metathesis product, wherein fatty oil base metathesis product can comprise that fatty oil base is from metathesis product.The candle of embodiment A, wherein metathesis product comprises the fatty acid-based metathesis product of polyol.The candle of embodiment A, wherein metathesis product comprises diprotic acid-polyol oligopolymer, described diprotic acid-polyol oligopolymer can comprise at least a dimer, tripolymer and the tetramer.This diprotic acid-polyol oligopolymer can comprise than dimer or the more tetramer of tripolymer and/or higher oligomers.The candle of embodiment A, wherein metathesis product has the fatty acid distribution (profile) that contains diprotic acid, and described fatty acid distribution (profile) can comprise than the more monounsaturated dicarboxylic acid of unsaturated dibasic acid.This diprotic acid can comprise than the more C18 diprotic acid of the diprotic acid with other length.Diprotic acid can be made up of the straight chain diprotic acid basically.The candle of embodiment A, wherein the fusing point of wax is about 45 ℃-Yue 70 ℃.The candle of embodiment A, wherein the iodine number of wax is not more than about 50 and be not more than about 20 usually.The candle of embodiment A, wherein wax further comprises petroleum wax.The candle of embodiment A, wherein wax further comprises natural wax.The candle of embodiment A, wherein candle wax has the fatty acid composition that contains 15:0 lipid acid.

The candle of embodiment A, wherein candle wax comprises at least a polyol fatty acid ester raw material, paraffin, lipid acid, carnauba wax and beeswax.The candle of embodiment A, wherein candle wax comprises polyol fatty acid ester raw material, for example part and/or all hydrogenant triacylglycerol ester raw material (for example, part and/or all hydrogenant vegetables oil).The candle of embodiment A, wherein candle wax comprises paraffin.The candle of embodiment A, wherein candle wax comprises lipid acid, for example stearic acid and/or palmitinic acid.The candle of embodiment A, wherein candle wax comprises carnauba wax and/or beeswax.The candle of embodiment A, wherein candle wax comprises polyol fatty acid ester raw material, described polyol fatty acid ester raw material can comprise glyceryl monostearate, monopalmitin or its mixture.

Candle (B), it comprises candle wick and contains the wax of diprotic acid-polyol oligopolymer.Polyol in this oligopolymer comprises glycerine and in some cases, can be made up of glycerine basically.The candle of embodiment B, wherein diprotic acid-polyol oligopolymer comprises at least a dimer, tripolymer and the tetramer.This diprotic acid-polyol oligopolymer can comprise than the dimer or the more tetramer of tripolymer.In some cases, can form by the ester of diprotic acid at least about the diprotic acid in half oligopolymer with at least 18 carbon.The candle of embodiment B, wherein wax has the acid distribution (profile) that contains diprotic acid.The candle of embodiment B, wherein candle wax has the fatty acid composition that contains 15:0 lipid acid.

The candle of embodiment B, wherein candle wax comprises at least a polyol fatty acid ester raw material, paraffin, lipid acid, carnauba wax and beeswax.The candle of embodiment B, wherein candle wax comprises polyol fatty acid ester raw material, for example part and/or hydrogenant triacylglycerol ester raw material (for example, part and/or all hydrogenant vegetables oil) fully.The candle of embodiment B, wherein candle wax comprises paraffin.The candle of embodiment B, wherein candle wax comprises lipid acid, for example stearic acid and/or palmitinic acid.The candle of embodiment B, wherein candle wax comprises carnauba wax and/or beeswax.The candle of embodiment B, wherein candle wax comprises polyol fatty acid ester raw material, described polyol fatty acid ester raw material can comprise glyceryl monostearate, monopalmitin or its mixture.

Candle (C), it comprises candle wick and has the wax of the acid distribution (profile) that contains diprotic acid.This wax can have a kind of acid and distribute (profile), and diprotic acid comprised than the more monounsaturated dicarboxylic acid of unsaturated dibasic acid during this acid distributed.The candle of embodiment C, wherein diprotic acid comprises the C18 diprotic acid of Duoing than the diprotic acid of other length.The candle of embodiment C, wherein wax comprises diprotic acid-polyol oligopolymer.The candle of embodiment C, wherein candle wax has the fatty acid composition that contains 15:0 lipid acid.

The candle of embodiment C, wherein candle wax comprises in polyol fatty acid ester raw material, paraffin, lipid acid, carnauba wax and the beeswax at least a.The candle of embodiment C, wherein candle wax comprises polyol fatty acid ester raw material, for example part and/or all hydrogenant triacylglycerol ester raw material (for example, part and/or all hydrogenant vegetables oil).The candle of embodiment C, wherein candle wax comprises paraffin.The candle of embodiment C, wherein candle wax comprises lipid acid, for example stearic acid and/or palmitinic acid.The candle of embodiment C, wherein candle wax comprises carnauba wax and/or beeswax.The candle of embodiment C, wherein candle wax comprises polyol fatty acid ester raw material, described polyol fatty acid ester raw material can comprise glyceryl monostearate, monopalmitin or its mixture.

Candle D, it comprises candle wick, and wax, wherein wax comprises by the basic material deutero-metathesis product that contains the triacylglycerol ester.The fusing point of wax is generally about 45 ℃-Yue 70 ℃.This metathesis product typically comprises the oligopolymer that contains the glycerine subelement; And have and contain one or more acid of planting alpha, omega-dibasic acid distributions (profile).Wax can have the fatty acid composition that contains 15:0 lipid acid.

The candle of embodiment D, wherein candle wax comprises at least a polyol fatty acid ester raw material, paraffin, lipid acid, carnauba wax and beeswax.The candle of embodiment D, wherein candle wax comprises polyol fatty acid ester raw material, for example part and/or all hydrogenant triacylglycerol ester raw material (for example, part and/or all hydrogenant vegetables oil).The candle of embodiment D, wherein candle wax comprises paraffin.The candle of embodiment D, wherein candle wax comprises lipid acid, for example stearic acid and/or palmitinic acid.The candle of embodiment D, wherein candle wax comprises carnauba wax and/or beeswax.The candle of embodiment D, wherein candle wax comprises polyol fatty acid ester raw material, described polyol fatty acid ester raw material can comprise glyceryl monostearate, monopalmitin or its mixture.

Candle wax (E), it comprises the hydrogenation metathesis product that is formed by the basic material that contains the polyol fatty acid ester (described polyol fatty acid ester has the fatty acid composition that contains at least a unsaturated fatty acids); With at least a in polyol fatty acid ester raw material, petroleum wax, lipid acid, carnauba wax and the beeswax.The wax of embodiment E, wherein the fusing point of candle wax is about 45-70 ℃ and about usually 55-65 ℃.The wax of embodiment E, wherein candle wax has the fatty acid composition that contains 15:0 lipid acid.The wax of embodiment E, wherein the hydrogenation metathesis product comprises hydrogenation TAG transposition oligopolymer.The wax of embodiment E, wherein the hydrogenation metathesis product comprises hydrogenation TAG transposition dimer.The wax of embodiment E, wherein the hydrogenation metathesis product comprises the hydrogenation TAG transposition tetramer.The wax of embodiment E, wherein the hydrogenation metathesis product comprises saturated C15-C24 hydrocarbon.The wax of embodiment E, wherein basic material comprises that iodine number is at least about 50 and be not more than about 20 vegetables oil in some cases.The wax of embodiment E, wherein the iodine number of candle wax is not more than about 50 and be not more than about 20 in some cases.The wax of embodiment E, wherein candle wax contains the hydrogenation metathesis product of the 10-40wt% that has an appointment.

The candle wax of embodiment E, it comprises stearic acid and/or palmitinic acid.The candle wax of embodiment E, wherein wax comprises glyceryl monostearate, monopalmitin or its mixture.The candle wax of embodiment E, wherein wax comprises paraffin.The candle wax of embodiment E, wherein wax comprises carnauba wax, beeswax or its mixture.The candle wax of embodiment E, wherein wax comprises hydrogenation polyol fatty acid ester raw material.The candle wax of embodiment E, wherein wax comprises polyol fatty acid ester raw material, for example part and/or all hydrogenant triacylglycerol ester raw material (for example part and/or all hydrogenant vegetables oil).The candle wax of embodiment E, wherein wax comprises paraffin.The candle wax of embodiment E, wherein wax comprises lipid acid (it comprises stearic acid and/or palmitinic acid).The candle wax of embodiment E, wherein wax comprises polyol fatty acid ester raw material, described polyol fatty acid ester raw material can comprise glyceryl monostearate, monopalmitin or its mixture.

Wax (F), it comprises:

The hydrogenation metathesis product that forms by the basic material that contains the polyol fatty acid ester (described polyol fatty acid ester has the fatty acid composition that contains at least a unsaturated fatty acids);

Polyol fatty acid ester raw material; With

Paraffin;

Wherein the fusing point of wax is about 55 ℃-70 ℃.

The wax of embodiment F, it comprises about 10-30wt% hydrogenant metathesis product; The paraffin of about 20-60wt%; With the triacylglycerol ester raw material of about 20-50wt% iodine number for about 0-70.The wax of embodiment F, wherein wax has the fatty acid composition that contains 15:0 lipid acid.

The wax of embodiment F further comprises stearic acid and/or palmitinic acid.The wax of embodiment F, wherein wax further comprises glyceryl monostearate, monopalmitin or its mixture.The wax of embodiment F, wherein wax further comprises carnauba wax, beeswax or its mixture.The wax of embodiment F, wherein wax further comprises hydrogenation polyol fatty acid ester raw material.The wax of embodiment F, wherein wax further comprises polyol fatty acid ester raw material, for example part and/or all hydrogenant triacylglycerol ester raw material (for example, part and/or all hydrogenant vegetables oil).The wax of embodiment F, wherein wax further comprises paraffin.The wax of embodiment F, wherein wax further comprises lipid acid (it comprises stearic acid and/or palmitinic acid).The wax of embodiment F, wherein wax further comprises polyol fatty acid ester raw material, described polyol fatty acid ester raw material can comprise glyceryl monostearate, monopalmitin or its mixture.

For some application that for example wherein may wish to produce by the extrusion molding technology candle, wax can have the fatty acid composition (the about 10wt%18:2 lipid acid of for example about 1-) that contains 18:2 lipid acid.This wax can have low relatively iodine number, for example is not more than about 25 and can comprise paraffin.Fatty acid composition in this wax generally includes 15:0 lipid acid.Fusing point is that the wax of about 140 ℉-150 ℉ (about 60 ℃-65 ℃) can be particularly suitable for compression molding.

For the application that wherein may wish to produce by the compression molding technology candle, wax can have and contains the very fatty acid composition of low levels polyunsaturated fatty acid (for example, being not more than about 2wt%18:2 lipid acid).Fatty acid composition in this wax can comprise 15:0 lipid acid.This wax can have low relatively iodine number, for example is not more than about 20 and more suitably be not more than approximately 10, and can comprise paraffin.Fusing point is that the wax of about 140 ℉-150 ℉ (about 60 ℃-65 ℃) can be particularly suitable for compression molding.Suitable example comprises the blend of wax; the blend of described wax comprises 10-30wt% hydrogenation metathesis product (for example hydrogenation metathesis product that is formed by vegetables oil, this soybean oil and/or Oleum Gossypii semen); the 20-50wt% iodine number (for example is not more than about 25 triacylglycerol ester raw material; hydrogenated vegetable oil) and the paraffin of about 20-60wt% (for example, fusing point is the paraffin of about 145 ℉-150 ℉).

Some embodiments of Wax composition of the present invention can be used basic wax, described basic wax can with other wax and additive blend, form the wax blend be suitable for as candle wax.For example, fusing point is at least about 55 ℃, and it is about 60 that iodine number is not more than, and comprises that the Wax composition at least about the triacylglycerol ester raw material of 50wt% triacylglycerol ester raw material and transposition can be used as this basic Wax composition.When the design candle wax is used for compression and/or during extrusion molding technology, basic wax can have lower a little iodine number requiredly, for example be not more than about 30 and more suitably be not more than about 15.The fusing point of this basic wax usually can be about 55 ℃-65 ℃, and is generally at least about 58 ℃.

In another embodiment, the fusing point of wax is that about 55 ℃-70 ℃ and iodine number are not more than about 25; Wherein wax comprises at least about 10wt%TAG transposition oligopolymer with at least about 50wt% triacylglycerol ester.The area ratio of (all TAG transposition oligopolymer)/(TAG transposition dimer) is generally at least about 3:1.

In another embodiment, it is about 25 that the fusing point of wax is that about 55 ℃-70 ℃ and iodine number are not more than, and comprise the oligopolymer of triacylglycerol ester, TAG transposition dimer, TAG transposition tripolymer and the TAG transposition tetramer and Geng Gao.This wax typically has the fatty acid composition that contains at least about 50wt%18:0 lipid acid.Based on area %, this wax also generally includes the oligopolymer than the TAG transposition dimer more TAG transposition tetramer and Geng Gao.This wax can comprise the TAG transposition oligopolymer of about 10-30wt% and the triacylglycerol ester of about 60-90wt%.This class wax can have low relatively iodine number requiredly, for example is not more than about 20 and use for some, and iodine number is not more than about 10.Design therein under the situation that wax is used for compression molding technology, its fatty acid composition can comprise the 18:2 lipid acid that is not more than about 2wt%.

It is about 75 that the fusing point of another embodiment of wax of the present invention is that about 50 ℃-70 ℃ and iodine number are not more than, and comprise the oligopolymer of triacylglycerol ester, TAG transposition dimer, TAG transposition tripolymer and the TAG transposition tetramer and Geng Gao.Based on area %, this wax can comprise the oligopolymer than the TAG transposition dimer more TAG transposition tetramer and Geng Gao; This wax can have to contain at least about the fatty acid composition of 50wt%18:0 lipid acid with for some to be used, and can wish to use the wax with fatty acid composition, and described fatty acid composition comprises the 18:0 lipid acid more than or equal to about 60wt%.The fatty acid composition of this wax can comprise the lipid acid of about 5-15wt%16:0.

An embodiment provides the wax with fatty acid composition again, and described fatty acid composition comprises the lipid acid at least about 2wt%15:0; Lipid acid at least about 50wt%18:0; Be not more than the lipid acid of about 2wt%18:2; With the alpha, omega-dibasic acid that has 18-24 carbon atom at least about 10wt%.The iodine number of this class wax can be not more than suitably about 15 and fusing point be about 55 ℃-65 ℃.This wax typically comprises the TAG transposition oligopolymer of about 10-30wt% and at least about the triacylglycerol ester of 60wt%.

With reference to various concrete and the embodiment that exemplifies and technical descriptions the present invention, yet, be to be understood that and can make many changes and remodeling, keep within the spirit and scope of the present invention simultaneously.

Claims (40)

1. Wax composition, it comprises:

(a) metathesis product that forms by the basic material that contains the polyol fatty acid ester, described polyol fatty acid ester has the fatty acid composition that contains at least a unsaturated fatty acids; With

(b) at least a in the following component: polyol fatty acid ester raw material, paraffin, lipid acid, carnauba wax and beeswax;

Wherein the fusing point of Wax composition is 20 ℃-70 ℃.

2. the Wax composition of claim 1, wherein the fusing point of Wax composition is 45 ℃-70 ℃.

3. the Wax composition of claim 1, wherein Wax composition has the fatty acid composition that contains 15:0 lipid acid.

4. the Wax composition of claim 1, wherein metathesis product comprises hydrogenation triacylglycerol ester metathesis product.

5. the Wax composition of claim 1, wherein metathesis product comprises the unsaturated hydrocarbons with 15-24 carbon atom.

6. the Wax composition of claim 1, wherein basic material comprises that iodine number is at least about 45 vegetables oil.

7. the Wax composition of claim 1, wherein basic material comprises soybean oil, low sinapinic acid rapeseed oil, plam oil, sunflower oil, Oleum Gossypii semen, rapeseed oil, butter, Toenol 1140, Semen Maydis oil, palm kernel oil, cocounut oil, lard, chicken fat or Yatall MA.

8. the Wax composition of claim 1, wherein wax comprises the metathesis product of 10-40wt%.

9. the Wax composition of claim 1, wherein wax comprises stearic acid, palmitinic acid, glyceryl monostearate, monopalmitin or its mixture.

10. the Wax composition of claim 1, its fusing point are that 55 ℃-70 ℃ and iodine number are not more than 30;

Wherein wax comprises the triacylglycerol ester transposition oligopolymer of 5wt% at least and the triacylglycerol ester of 50wt% at least.

11. the Wax composition of claim 10, wherein wax comprises than the triacylglycerol ester transposition dimer more triacylglycerol ester transposition tetramer and high-grade oligopolymer more.

12. the Wax composition of claim 1, its fusing point is not more than 30 at least 55 ℃ with iodine number; Wherein wax comprises the triacylglycerol ester raw material of 50wt% triacylglycerol ester raw material and transposition at least.

13. the Wax composition of claim 12, wherein triacylglycerol ester raw material comprises hydrogenated vegetable oil; Comprise hydrogenation transposition vegetables oil with the triacylglycerol ester raw material of transposition.

14. the Wax composition of claim 13, it comprises the hydrogenation transposition vegetables oil of 10-50wt%; At least the hydrogenated vegetable oil of 50wt%.

15. the Wax composition of claim 12, its iodine number is not more than 15.

16. the Wax composition of claim 12, it has the fatty acid composition that contains 5-15wt%16:0 lipid acid.

17. the Wax composition of claim 12, wherein wax has the fatty acid composition of the alpha, omega-dicarboxylic acid that contains at least a 18-24 of a having carbon atom.

18. the Wax composition of claim 12, wherein wax comprises 15:0 lipid acid.

19. the Wax composition of claim 12, wherein wax comprises that the 50wt% iodine number is not more than 15 hydrogenated vegetable oil at least; Be not more than the hydrogenation metathesis product that 15 vegetables oil raw material forms with 10-40wt% by iodine number.

20. the Wax composition of claim 12, wherein wax comprises the complete hydrogenant soybean oil of 50wt% at least.

Be not more than 25 21. the Wax composition of claim 10, its fusing point are 55 ℃-70 ℃ and iodine number, wherein wax comprises:

At least 5wt% triacylglycerol ester transposition oligopolymer; With

At least 50wt% triacylglycerol ester.

22. the Wax composition of claim 21, it comprises the triacylglycerol ester transposition oligopolymer of 10-25wt%.

23. the Wax composition of claim 21, it comprises the hydrogenation metathesis product that 10-40wt% is formed by vegetables oil.

24. the Wax composition of claim 1; it is about 75 that its fusing point is that 50 ℃-70 ℃ and iodine number are not more than, and comprise: triacylglycerol ester, triacylglycerol ester transposition dimer, triacylglycerol ester transposition tripolymer and the triacylglycerol ester transposition tetramer and high-grade oligopolymer more.

25. the Wax composition of claim 24, its iodine number is not more than 25.

26. the Wax composition of claim 24, it has and contains the fatty acid composition that is not more than 2wt%18:2 lipid acid.

27. the Wax composition of claim 24, it has the fatty acid composition that contains 15:0 lipid acid.

28. the Wax composition of claim 24, wherein wax comprises:

The triacylglycerol ester transposition oligopolymer of 10-30wt%; With

The triacylglycerol ester of 60-90wt%.

29. the Wax composition of claim 24, it has the fatty acid composition that contains 5-15wt%16:0 lipid acid.

30. the Wax composition of claim 24, it has and contains the fatty acid composition of 10wt% diprotic acid at least.

31. the Wax composition of claim 30, wherein diprotic acid comprises alpha, omega-dibasic acid.

32. the Wax composition of claim 24, it has and contains the fatty acid composition of 60wt%18:0 lipid acid at least.

33. the Wax composition of claim 24, its iodine number is not more than 10.

34. the Wax composition of claim 24, its fusing point are 55 ℃-65 ℃.

35. the Wax composition of claim 1, it comprises:

By the hydrogenation metathesis product that the basic material that contains the polyol fatty acid ester forms, described polyol fatty acid ester has the fatty acid composition that contains at least a unsaturated fatty acids;

Polyol fatty acid ester raw material; With

Paraffin;

Wherein the fusing point of Wax composition is 45 ℃-70 ℃.

36. the Wax composition of claim 35, wherein the fusing point of wax is 55 ℃-70 ℃.

37. the Wax composition of claim 35, it comprises:

The hydrogenation metathesis product of 10-30wt%;

The 20-50wt% iodine number is not more than 70 triacylglycerol raw material; With

The paraffin of 20-60wt%.

38. the Wax composition of claim 37, wherein wax comprises the paraffin of 40-50wt%.

39. the Wax composition of claim 35, wherein wax has the fatty acid composition that contains 15:0 lipid acid.

40. the Wax composition of claim 35, wherein the iodine number of wax be not more than 25 and fatty acid composition comprise 2-10wt%18:2 lipid acid.

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