TWI322180B - Partial acyl glyceride based biowaxes and candles prepared therefrom - Google Patents

Description

IX. Description of the Invention: [Technical Field] The present invention relates to a raw butterfly which comprises a partial mercaptoglyceride (PAG), and the present invention also relates to a biotin butterfly formed by the raw butterfly, and A method of making them. [Prior Art] Many types of candles have been developed on the market, and in the prior art, 'wax candles are made of paraffin wax and/or natural wax. Some typical candelas made by conventional methods can be formed into a cup candle, a votive candle, a pillar candle, a tape candle, Tea-light candles and hurricane candles ° For a long time, raw waxes such as beeswax (myricyl palmitate) and butterfly (myricyl palmitate) have been known. (cetyl palmitate)), etc., can be used as a natural wax for making candles. Recently, with the development of the petroleum refining industry, fossil waxes, such as sarcophagus, can also be used as raw materials for waxy waxes for the manufacture of candles. Today, paraffin-based waxes are the main source of raw materials for the manufacture of candles. These paraffin waxes are made from residues left after refining of fossil oils. It has been found that paraffin wax can be completely burned, but when it burns' Smoke is usually released and an unpleasant odor is produced. Palm stearin is a by-product from the net oil refining industry. The annual yield of palm stearin is very large, and its price is much cheaper than that of stone sacrifice. Try to use palm stearin as a component of candle wax. . However, due to the fact that palm stearin has a lower refining point, its blending percentage in the sputum is limited and difficult to control. Even if the palm kernel stearin can be hydrogenated into a more dazzling palm stearin, the candle made from it is more fragile and lacks malleability. Therefore, the application of palm stearin as a component of candle wax is still limited. In order to provide candles having clean burning characteristics, a wide range of studies have been conducted on candle waxes having a low paraffin content, for example, U.S. Patent No. 6,503,285 ' 6,645,261 > 6,770,104'6,773,469 ' 6,797,020 > and 6,824,572 all disclose tridecyl glycerol. Bottom candle wax, especially candle wax derived from various animal sources and/or plant sources such as vegetable oil sources. However, candle waxes formulated from vegetable oil-based materials often cause various problems. Candles based on vegetable oils have been found to have a number of disadvantages compared to paraffin-based candles, such as crack formation of air pockets (air 〇 e P ' 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 。 。 。 。 。 。 。 。 Waxes based on 2 ugly have problems associated with the following properties: the most appropriate flame size, the performance of waxes and wicks that are effective for uniform combustion, maximum dryness; when L, the color integration of the product and/or The shelf life of the product. Therefore, to make the product aesthetic and functional, the surface of the product and the quality required by the consumer 'need to develop a new vegetable oil-based replacement 壌. Μ 有 有 有 开发 开发 开发 开发The material forming the crucible (four) I substitute has clean combustion properties, preferably, the biodegradable and derived from the recycled raw material, and more preferably, the candle matrix wax material has the following physical properties: for example, making the material easy Forming a melting point, hardness and/or ductility of a candle with a pleasant appearance and/or feel, and having an ideal olfactory property. Further, the Kyoto Protocol has established The treaty on green issues in various aspects is intended to 'stabilize the concentration of greenhouse gases in the atmosphere to prevent the risk of interfering with the anthropogenic content of the climate system.” Due to the shortage of fossil fuel sources and oil prices Continued deepening, biomass fuels play a very important role in the renewable energy supply chain. In the rapidly developing biodiesel supply chain, the excess supply of glycerol becomes an urgent problem to be solved. The present invention provides a biomass wax based on a partially fluorenyl glyceride (pAG). The PAG-based biomass wax can consume a large amount of glycerin, so that it can be combined with the biodiesel supply chain. The invention solves the problem of excessive production of glycerin. In the present invention, the consumption of glycerin to produce a PAG-based raw butterfly and the use of the raw wax to form an environmentally friendly candle will contribute to the normal development of the carbon cycle system on the earth. Guiding petroleum energy is an extremely valuable and feasible agricultural energy policy. The present invention provides a PAG-based biomass wax suitable for use as a wax. Wax. In terms of flame length, the PAG-based biomass bad candle has a burning characteristic compared to a commercial candle made of paraffin, and does not have an unpleasant odor. Compared with paraffin The wax has excellent characteristics 'including low black smoke emission and high additive compatibility, which makes the Pag-based biomass wax effectively replace the paraffin. According to the present invention, the present invention further provides a raw candle. The invention comprises a raw material wax and a wick, wherein the raw material wax comprises a partial mercaptoglyceride. Further, the candle may be formed by a PAG-based raw material wax containing paraffin and/or hard fat ( Stearin) As an additional ingredient, the candle made from it exhibits a uniform composition, translucent and fine-grained crystal structure, which usually burns cleanly and releases a very small amount of black smoke. The candle of the present invention is a particularly environmentally friendly product due to the combination of low black smoke emission and biodegradability, and a candle made of recycled raw materials. According to the present invention, there is provided a method of producing a raw candle which can be formed into various types of raw candles such as cup-shaped wax candles, candle beads and the like by the method of the present invention. [Embodiment] According to the present invention, the raw wax comprises a partially mercaptoglyceride (PAG), and preferably, the bio-derived wax according to the present invention contains about 20% by weight to 1.5% by weight to 100% by weight. / 〇, preferably 30 weight ° / ❶ to 100% by weight of PAG, based on the total weight of the raw wax. As used herein, the term "raw wax" means a wax made from a raw material derived from a raw rubber supply chain. As used herein, the term "partial thioglycolic vinegar" means a glycerin S selected from the group consisting of monomercaptoglycerol (MAG), dimercaptoglyceride (DAG), and combinations thereof. The moiety thiol glycerol S can be prepared by esterification of a glycerol molecule with one or two medium or long chain fatty acids. As used herein, the term "medium chain fatty acid" 1322180 means a saturated or unsaturated fatty acid having 6 to 10 carbons, or a mixture thereof, and the term "long-chain fatty acid" means having a saturation of 14 to 24 carbons. · ' or unsaturated fatty acids, or a mixture thereof. More preferably, the thiol has a linear chain of C16, C18, C18:1, C18:2. According to the invention, the partially mercaptoglyceride 5 can be used alone or in combination with a trimethyl glyceride and/or other ingredients. The term "biomass candle" as used herein refers to a candle made from raw wax. According to the present invention, the raw wax may further comprise tridecyl glyceride (TAG), hard moon or paraffin, or a combination thereof as an additional component. In a preferred embodiment of the present invention, the raw material wax comprises monodecyl glyceride 10 (MAG), dimercapto glyceride (DAG) and tridecyl glyceride (TAG) fluorenyl monoglyceride. A preferred amount is from about 10 to 75% by weight, more preferably from about 40 to 70% by weight, based on the weight of the raw butterfly. The dimercaptoglycerol (DAG) is preferably used in an amount of from about 10 to 50% by weight, more preferably from about 10 to 35% by weight, based on the weight of the raw wax. The tri 15 decyl glyceride (TAG) may optionally be used in an amount of from about 5 to 50% by weight, preferably from 10 to 40% by weight, based on the weight of the raw wax. In the present invention, the raw wax may optionally include a small amount of other additives to modify the properties of the waxy material. Examples of additives which may be incorporated into the raw wax of the present invention include: colorants, perfumes (e.g., essential oils), antioxidants, 20 UV light absorbers and mobile inhibitors, and the like. Preferably, the biomass is blended with a natural colorant to provide a uniform monochromatic distribution. The raw wax has a melting point of about 40 to 62 ° C. In one embodiment, the raw wax has an iodine value of from about 0.2 to about 35. In the present invention, the raw wax can form a desired shape. According to a preferred embodiment, the raw wax can form a powder or granules. Preferably, the raw wax can form beads, which can be obtained by heating the raw wax into a molten state and then spraying and cooling the molten raw wax, or can be purchased from Chengde Oil Co., Ltd. (Chant Oil Co., Ltd. (China Republic of China Taiwan) made of beads manufacturing equipment. According to the present invention, the raw wax can be formed into beads having a diameter of about 0.5 to 1.2 mm. In the present invention, the raw material wax is suitable as a raw material for producing a raw candle. According to the present invention, there is provided a raw candle comprising a raw wax and a wick, wherein the raw wax comprises a partially mercaptoglyceride (PAG). Biomass candles are essentially solid, stable and not brittle, and are usually somewhat malleable, with no visible free oil. In the present invention, the raw candle can be formed into a desired shape of a candle by a melt-processing method, such as a columnar candle, a tea butterfly candle, or the like. In the present invention, in order to be able to fully benefit from the field of environmental safety of the PAG-based biomass wax, it is desirable to use a wick having no metal core (e.g., lead or zinc core). An example of a suitable wicking material is a braided cotton core. The wick can also be used with standard wicks for other waxes such as paraffin and/or beeswax. According to the present invention, there is further provided a method of producing a green candle comprising the steps of: 1) heating a PAG-based biomass wax to a molten state, and 2) introducing the molten biomass wax into a mold, wherein the mold A wick is included therein, 3) cooling the molten raw wax in the mold, and 4) curing the raw wax, and then removing the cured raw wax from the mold. The present invention further provides a method of manufacturing a raw candle comprising heating a PAG-based biomass wax to a molten state, spraying and cooling the raw wax to form 0.5 to 1.2 mm beads, and the raw material The wax beads are pressed into a mold to form a candle. In the process of a raw candle, it is important that the color former, if present, be dissolved in the PAG-based biomass wax to prevent insoluble particles from blocking the flow of the raw wax in the wick. Usually, the blocked wax stream will produce poor candle burning. Furthermore, the color of the raw wax may also affect the dyeing performance. Most of the perfume can be used in the raw wax to improve the quality of the resulting biomass, such as stability, reactivity, color and the like. According to the present invention, the produced raw candle can cleanly burn and release a very small amount of black smoke. In the present invention, it is to be understood that all numbers of ingredients, properties, and the like, which are represented in all examples of the specification and claims, are modified by the word '', and all parts and percentages mean by weight unless otherwise The invention is described in more detail by the following examples, which are not intended to limit the scope of the invention in any way, although the numerical ranges and The numerical values in the examples. However, any numerical value inherently contains a certain deviation, which is a standard deviation which must be produced in each test test. Example A. Gas Chromatographic Analysis of PAG

GC Model: YOUNGLIN ACME 6000M GC 1322180 GC conditions: 1. Column: QUADREX fusion meteorite capillary column;

007-65HT-25W-0.1F, 0.32mmID

2. Detector: FID 3. Carrier gas: nitrogen 4. Oven temperature:

10

1) 80 ° C (maintained for 1 minute), and reached 240 ° C at a rate of 20 ° C / minute

2) 240 ° C, and reach 360 ° C at a rate of 4 ° C / min 3) 360 ° C (maintain 11 minutes)

5. Injector temperature: 280 ° C

6. Detector temperature: 360 ° C

7. Measurement range: 6xl03mV 15 Preparation of sample: Mix 0.2 g sample uniformly with 5 ml gas. Analytical conditions: 1. Sample amount: 0.2 μl 20 2. Analysis time: 50 minutes B. Ingredients for preparing wax Component 1: Paraffin wax, supplied from Taiwan Wax Co., Ltd. It has physical properties as shown in Table 1. 1322180

5 Table 1 Physical properties Test method Value MP > °C ASTM D87 59.8 Needle puncture at 25 ° C, mm ASTM D1321 15.5 Dynamic viscosity at 100 ° C, cps ASTM D445 4.382 Oil content, wt% ASTMD721 0.116 Color ASTM D156 30 Carbon distribution ASTM D5442 〇20~C46 〈. 26 16.48% C26-29 23.78%. 29-32 23.05% C32*44 36.69% >C々4 nil η-stone butterfly 51.05% Ingredient 2: Fatty acid S1801, supplied from P.T. MUSIM MAS., having physical properties as listed in Table 2. Table 2 Physical properties Test method Numerical acid value, mg KOH / gram ASTM D 1980-87 210.2 Saponification value, mg KOH / gram ASTM D1962-85 211.4 Iodine value, gram iodine / 100 g ASTM D 1959-97 0.13 -13 - 1322180 Composition 3: Fatty acid 1698, supplied from PT MUSIMMAS., having the physical properties as listed in Table 3. 5 Table 3 Physical Properties Value Acid value, mg KOH / g 218.5 Saponification value, mg KOH / g 220 Iodine value, gram iodine / 100 g 0.1 M.P.,. C 62.0 Fatty acid carbon chain composition, % C12+14 0.3 C16 98.6 C18 1.1 Other 0.5

MP > °C ASTMD 1982-85 55.4 Fatty acid carbon chain composition, % ASTMD 1983-90 C12+14 0.4 C16 57.67 C18 41.3 Other 0.5 Ingredient 4: Two types of RBD palm 櫊 stearin, supplied from PT MUSIM MAS., Has the physical properties as listed in Table 4. 1322180

Table 4 Physical Properties Type 1 Type 2 Free fatty acids, % 0.057 0.01 Moth, Moth/100 g 20.4 33,3 M.P.,. C 56.5 51 Fatty acid carbon chain composition, % C16 72.00 59.8 C18 5.10 3.67 C18:l 16.22 29.7 C18:2 3.67 5.22 Ingredient 5: Hardened fat F081, from RBD palm stearin (type 2, into 5 points 4) at temperature The hydrogenation reaction was carried out for 4 hours in the presence of 170 to 200 ° C under a pressure of 3 kg and a nickel catalyst (0.2%), and had the physical properties as listed in Table 5.

Table 5 Physical Properties Value Acid value, mg KOH / g 1.2 Saponification value, mg KOH / g 196.8 Iodine value, gram iodine / 100 g 0.4 M.P.,. C 57 Color Gardner 1.3 -15- 1322180 Ingredient 6: Partially fluorenyl glyceride defined as GMP, reacted with 200 g of fatty acid 1698 (ingredient 3) and 72 g of glycerol at 250 ° C for 5 hours. The producers have the physical properties as listed in Table 6a, and the GC analysis results and data are shown in Figures 1 and 6b, respectively. Table 6a Physical Properties Values Free fatty acids, % 1.2 M.P. > °C 56 MAG, % 64.0 DAG, % 25.5 TAG, % 9.3 MAG : monodecyl glyceride DAG : dimercapto glyceride

Fatty acid carbon chain composition, % C16 59.8 C18 38.6 10 TAG : Trimercaptoglyceride Table 6b Peak number component retention time (seconds) Area percentage (%) 1 FFA 8.813 146.88 1.20 2 GMP 14.424 7845.39 63.98 3 GDP 31.754 3132.86 25.54 -16 - 1322180 4 GTP 48.118 1137.85 9.28 FFA: free fatty acid GMP: monopalmitin glycerol GDP: glyceryl dipalmitate GTP: glyceryl tripalmitate

10 Ingredient 7: A partial mercaptoglyceride defined as GMSIV=1.(), prepared by reacting 200 g of fatty acid S1801 (ingredient 2) with 72 g of glycerol at 250 ° C for 5 hours. The physical properties listed in 7a, GC analysis results and data are shown in Figure 2 and Table 7b, respectively.

Table 7a Physical properties Numerical acid value, mg KOH / gram 0.4 Iodine value, gram iodine / 100 g 0.2 color, APHA 140 MP > °C 56 MAG > % 62.6 DAG, % 28.8 TAG, % 7.6 Table 7b Peak number component Residence time (seconds) Area percentage (%) 1 G 3.539 519.91 0.65 2 FFA 6.525 233.16 0.29 3 FFA 7.350 46.61 0.06

1322180 4 Mono-glycerol 6 10.453 48623.36 60.90 5 Di-glyceride 16.861 215.56 0.27 6 Di-glyceride 23.320 24237.86 30.36 7 Tri-glyceride 36.047 5964.83 7.47 G: Glycerol component 8: Partially defined as GMSIV=15 Glyceryl ester prepared by reacting 200 g of a mixture of equal amounts of F081 (ingredient 5) with RBD palm stearin (type 2, ingredient 4) with 40 g of glycerol at 250 ° C for 8 hours, as shown in Table 8a The listed physical properties, GC analysis results and data are shown in Figures 3 and 8b, respectively.

Table 8a Physical property values MP > °C 46 MAG,% 68.35 DAG,% 15.69 TAG,0/〇11.72 Peak number Component retention time (seconds) Area percentage (%) 1 G 2.572 83.89 0.62 2 FFA 6.424 487.76 3.61 3 FFA 7.287 558.61 4.14 -18- 1322180 _ Ingredient 9: Partially defined as GMSlv=2〇 Part of thiol glycerol, reacted by 200 g of RBD palm stearin (type 1, ingredient 4) with 40 g of glycerol at 250 ° C The physical properties were obtained as shown in Table 9a for 8 hours, and the GC analysis results and data are shown in Figures 4 and 9b, respectively.

4 mono-glyceride 9.360 8665.79 64.21 5 di-glyceride 15.445 10.99 0.08 6 di-glyceride 19.710 2106.60 15.61 7 tri-glyceride 27.898 6.40 0.05 8 tri-glyceride 29.627 42.31 0.31 9 tri-glyceride 31.626 1532.99 11.36 Table 9a Physical properties Numerical color 1.4 MP - °C 46 MAG > % 49.6 DAG, % 11.1 TAG, % 33.1 Table 9b Peak number component retention time (seconds) Area percentage (%) 1 FFA 6.499 989.15 5.25 2 Mono-glyceride 9.405 8776.13 46.60 c S ) -19- 1322180 3 Di-glyceride 19.948 2471.18 13.12 4 Tri-glyceride 27.846 16.10 0.09 5 Tri-glyceride 32.311 6582.08 34.95 Ingredient 10: Partially fluorenyl glyceride defined as GMSIV=30, from 200 The grams of RBD palm stearin (type 2, from component 4) were prepared by reacting 40 grams of glycerol at 250 ° C for 8 hours, with physical properties as shown in Table 10a. GC analysis results and data are shown separately. 5 and Table 10b.

Table 10a Physical property values MP - °C 42 MAG > % 66.2 DAG > % 13.4 TAG > % 13.3 Table 10b Peak number component retention time (seconds) Area percentage (%) 1 G 2.489 49.89 0.18 2 FFA 6.511 1933.86 6.93 3 mono-glycerol vinegar 9.507 18463.30 66.20 4 di-glyceride 13.502 14.22 0.05 5 di-glyceride 15.504 20.38 0.07 6 di-glycerol vinegar 20.023 3715.59 13.32 -20- 1322180 C. Preparation of cup-shaped candles to be tested (see Table 11) Listed): Mix equal amounts of different bismuth ingredients and heat to smelt. The fused wax was poured into an aluminum cup having a height of 15 mm X and a diameter of 37.5 mm, and a 23 mm long braided wick in the middle of the cup. The resulting woven fabric is cooled and solidified for use in a combustion test. Example 1 $ A cup-shaped candle was prepared according to the ingredients and contents listed in Table 11. 10

7 Tri-glyceride 27.924 18.28 0.07 8 Tri-glyceride 33.699 3674.74 13.18 D. Combustion test. Biomass butterfly candle made from biomass wax based on partial mercaptoglyceride (PAG), its combustion properties By the following steps: y the number and weight of the cup-shaped candles containing different amounts of wax components; ·=cup-嘱 on the test bench, placed in millimeters; *Magnetism: plate on the table Above 75 mm high to observe the black smoke released by the smoldering candle during burning; 4 m type and start timing; when there is a circle of soil around each turbid core, 5 times for 1 to 6 minutes), measure each as soon as possible The flame height of the cup type _; • the flame height is measured once in the hour; 1 after 60 minutes, the flame temperature of each cup type ant is measured at the highest point of the inner flame 20 1322180 7. After any of them burns completely, all flameout , weigh each type of candle; then calculate the burning rate of each type of candle. The results of the burning test of the cup-shaped candle are shown in Table 11. Table 11

Example No. 1 2 3 4 5 6 7 8 9 (Scare) 10 11 12 13 Ingredient 1: Paraffin (weight, gram) 3.91 4.94 5.23 7.78 7.49 Ingredient 2: Sl8〇l (weight, gram) 3.91 4.94 5.49 7.99 7.49 Ingredients 5 : F081 (weight, gram) 3.91 5.23 5.49 7.78 Ingredient 6 : GMP (weight * gram) 21.59 Ingredient 7 : OviStvHfl (weight, gram) 3.91 4.94 5.23 5.49 7.99 7.78 7.78 15.32 Composition 8: αν^15 (weight, gram) 23.26 Component 9: CMW weight, gram) 22.87 Component KTGMW weight, Magic 22.04 Properties MPfC) 50.5 52 52 5Ϊ.5 52 53 57.5 54 52 46 46 42 52 Initial weight (g) 15.64 】4.82 15.69 16.47 15.98 15.56 15.56 15.32 14.98 23.26 22.87 22.04 21.59 Residual weight (g) 丨 32 minutes later 4.77 3.10 3.64 6.76 7.37 5.60 2.78 3.62 3.88 14.24 14.00 15.11 10.60 Burning rate (g/hr) 4.94 5.32 5.48 4.42 3.91 4.53 5.80 5.32 5.04 4.10 4.03 3.15 5.00 Flame temperature fc) 731 768 757 711 729 777 839 881 806 835 740 668 820 Flame height (mm), after 6 cents 26 27 25 23 24 24 27 22 33 15 25 20 25 Flame height (ΐ米), 70 points i childhood 26 26 26 22 15 25 30 22 28 18 18 10 18 Flame height (mm V丨32 cents after 21 24 30 20 15 23 23 21 27 15 17 6 24 As shown in Table 11, the raw candle made of the raw material wax of the present invention is used together with the paraffin wax and/or hard fat measured by the flat 222.1180, which exhibits excellent (four) characteristics of the flow through the mail' Hair quality 2 蜀 及 及 及 及 及 及 ( ( ( ( ( ( ( 四 ( ( 四 四 四 四 四 四 ( ( 四 四 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 破Hair: ^, the scope of the attached patent application, and (4) the changes in the meaning and scope of the equivalent are covered. Ίο 15 20 [Simple description of the drawing] Fig. 1 shows the results of gas chromatography analysis of GMP of Example 13. C shows the results of gas chromatographic analysis of a part of mercaptoglyceride (defined as GMS丨...) of Example 8. Figure 3 shows the results of gas chromatographic analysis of a portion of the glyceryl vinegar of Example 10 (defined as (4) (iv)). Figure 4 shows the results of gas chromatographic analysis of a portion of glyceryl vinegar (defined as gms (4)) of Example u. Figure 5 shows the results of gas chromatographic analysis of a part of mercaptoglycerol vinegar of Example 12 (defined as (iv) 丨 (4)). [Main component symbol description] (none) -23.

Claims (1)

X. Patent application scope: 1. A raw material wax containing a part of mercaptoglyceride as a main component, the composition of which comprises 55 to 95% by weight of partial mercaptoglyceride, based on the total weight of the raw wax; The glycerin S is intended to include a group of monodecyl glycerin vinegar, di-branched glycerin, and combinations thereof. 2. The raw material wax according to claim 1, wherein the amount of the monomercaptoglyceride is 45 to 70% by weight, and the content of the diacid glycerin is 10 to 35% by weight, based on the raw wax. The total weight is the basis. 3. The raw material wax according to claim 1 of the patent application, further comprising tridecyl glyceride, the trimethyl glyceride content being 5 to 40% by weight based on the total weight of the raw wax. 4. The biomass wax according to item 3 of the patent application, which has a melting point of about 40 to 62 ° C and an iodine value of about 0.2 to 35. 5. A candle comprising a raw wax having a partial mercapto glyceride as a main component, and a wick, wherein the composition of the raw wax comprises 55 to 95% by weight of a part of the thioglycolic vinegar, and the total of the raw butterfly Based on the weight; part of the mercaptoglycerol is intended to comprise a group of mono-branched glycerol, dimercaptoglycerol, and combinations thereof. 6. The candle according to item 5 of the patent application, wherein the content of the monoterpene glyceride in the raw material wax is 45 to 70% by weight, and the content of the dimercaptoglyceride is 10 to 35% by weight, in the raw material. The total weight of the wax is the basis. 7. The candle according to claim 5, wherein the raw material wax further comprises tridecyl glyceride, and the tridecyl glyceride is present in an amount of 5 to 40% by weight based on the total weight of the raw wax. 8. The candle according to item 7 of the patent application, wherein the raw material wax has a melting point of 1322180 * b of about 40 to 62 ° C and an iodine value of about 0.2 to 35.