JPH01502193A - Propoxylated Guerbet alcohol and its esters - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Propoxylated Guerbet alcohol and its ester The present invention has one aspect. Regarding novel compounds derived from guerbet alcohol. It is. Another aspect relates to a method for producing the novel compound, and others. A composition containing the novel compound and the composition as a lubricant It is about using.

Background of the invention Water-insoluble oils such as mineral oils or unsaturated fatty oils are preferred for metalworking due to their cooling efficiency. It is well known that it is not completely accepted. Fli No. 3,929,656 (December 30, 1975) The period patent covers 60-90% mineral oil, 5-30% unsaturated fatty oil and 3-30% paraffin oil. A representative oil based on a system consisting of 15% is disclosed. This kind of oil is the main ingredient Emulsion type lubricants are used for hot rolling, drawing and ironing of aluminum. Includes manufacturing of aluminum cans by ironing, cold rolling of steel, etc. It has been traditionally used for plastic deformation processing. These traditional emulsions are milk anionic soaps, nonionic surfactants such as alkoxylated alcohols, Contains sorbitol esters, and other additives. used for these processes Typical products are liquids at ambient temperature and exhibit the required lubricating properties. It has such a high molecular weight. Obtain a lubricating substance that is highly effective and is a liquid. However, the products of interest are oleic acid, leruric acid, and tall oil acid. Based on saturated hydrophobes. Sugya U.S. Patent No. 3.945.930 (1 March 23, 976) are nonionic fatty acid ethoxylates and oil-soluble unsaturated fats. Typical emulsion system consisting of triglyceride and phosphate ester corrosion inhibitor is disclosed. U.S. Patent Nos. 4.042.515 and 4.075.39 No. 3 contains dimer acid unsaturated fatty acid ester used in emulsion systems for metal lubrication. is listed.

Applying a hydrophobic coating to preformed aluminum is covered by U.S. Patent No. 4.243.537, 4.362.634 and 4.581.15 No. 2, in which water-dispersible unsaturated fatty acid alkoxylates and Alkanolamine soap is a drawing compound. d) used in

The above-mentioned substances act fairly well as lubricants, but they oxidize and give off bad odors.

Additionally, the double bonds necessary for the desired fluidity may be oxidized to form low molecular weight aldehydes, ton and condensation products, and these products react to produce by-products and Provides a pleasant colour, odor and taste. At a very small concentration of ppm, it becomes a by-product. These harmful consequences therefore remain even after repeated cleaning. Such failure Advantageous properties include molded metal containers using such synthetic lubricants during the manufacturing process. Particularly unacceptable for filling beverages or other foodstuffs . In the brewing industry, synthetic lubricants have recently been used as synthetic lubricants during the manufacture of metal containers. The maximum unsaturation level indicated by the iodine value of KOH of 3/g was taken for the quality.

Therefore, the object of the present invention is to overcome the drawbacks of the above-mentioned lubricants and to provide a suitable solution for lubrication during metal forming. The objective is to provide a convenient and effective economical method for

Another object of the invention is to provide a group of compounds with excellent lubrication properties and low unsaturation levels. It's about providing things.

Another object of the present invention is to provide a relatively high-quality material which retains fluidity at temperatures suitable for metal processing. The objective is to provide a small amount of lubricant.

Yet another object of the invention is to provide a lubricant particularly useful in the manufacture of aluminum cans and sheet metal. An object of the present invention is to provide a lubricant composition.

invention In the present invention, the following formula: (wherein R and R1 are each independently an alkyl group having 1 to 20 carbon atoms) group, and the total number of carbon atoms of R + R' is 4 or more; y is a number from 1 to 20; Indication: The sum of integer X and integer 2 is O~20; R2 is a hydrogen atom, an alkyl group, or or -COR3 group, and R3 is a hydrogen atom, an unsubstituted alkyl group, or an alkyl group. Kenyl group, carboxyl group, COR' group or the following formula: An alkyl group or alkenyl group substituted with a cyclohexenyl group represented by and m represents a number from 1 to 3: n represents a number from θ to 10: p and r represent that Each represents the number of θ to 1: R3 is a hydroxyl group or the following formula: represents an alkoxylated Guerbet group represented by: Rs has 1 to 10 carbon atoms; (indicating an alkyl or alkenyl group) Provides alcohol and its esters. These compounds are in their pure state. It can be used as a lubricant alone or in the form of a mixture, and mineral oil, such as water, alkoxylated or unalkoxylated paraffin oils and esters. It can be blended into a composition containing an inert solvent such as. Also, lubricant composition The substance contains less than 50% by weight of the Guerbet derivative compound represented by formula A. It may contain guerbet alcohol and Cannizzaro soap by-products.

The compounds of formula A have a low impurity value with an iodine value of less than 7, preferably less than 2. It is a compound with a degree of saturation. The most preferred compounds of the present invention have unsaturation. Compounds that have no iodine value and compounds that have an iodine value of almost zero. Compound of the present invention The presence of propylene oxide in it is important. The reason is that Lopylene oxide gives the lubricant the required high fluidity and allows it to withstand ambient temperatures and above. This is because it maintains a liquid state at low temperatures. In this way, propylene oil The presence of oxide (PO) units indicates that alkoxylation occurs only with ethylene oxide (EO). impart significantly greater fluidity to the purified Guerbet derivative product. EO units and Although the PO units are mainly distributed in blocks, there are intervals in the polymer chain. can be made to exist randomly. Preferred for use in metal forming New compounds are those containing significant amounts of P units.

Unless otherwise specified below, temperatures are given in °C and percentages and ratios are given by weight; Pressure is expressed in kg/cm" absolute pressure (psia). Guerbet alcohol is beta A compound having a branch on a carbon atom, with the following formula: (R and R1 in the formula are the same as those described above).

Preferred products of the invention are alkyl radicals in which R and R' have from 6 to 15 carbon atoms. represents a group; y represents a number of 1 to 1O, most preferably a number of 2 to 8; represents a number whose sum is from 2 to 20, most preferably from 4 to 10; A compound whose degree of unsaturation is less than 2. In most cases, the 20 part is dominant However, the presence of the 20-moiety improves the fluidity, detergency, and important for oxidation resistance and oxidation resistance. Furthermore, in the above formula A, R2 represents an organic group. and preferably this group has 4 or more carbon atoms.

As mentioned above, the compounds of the present invention, alone or as a combination, can be used for molding metal containers, automatic Cast molding of car instrument panels, especially car bumper molding by RIM method, Metals, thermoplastics and rubber materials, such as cast molding of rubber tires It can be used for molding, fluid molding and extrusion molding. When forming containers The operations involved in this include cupping, canning, and anning), rolling, forging, ironing, drawing, corrugating (wrin kling) etc. In all of these operations, the compound of the invention is Metal or thermoplastic or rubber that acts as a lubricant and is subject to deformation. It is possible to quickly and cleanly demold the molded product by applying it to the mold to be injected. . Used in such operations when pouring thermoplastics and rubbers The advantage of the compound of the present invention is that the compound of the present invention performs its action externally and It is possible to attach it directly to the mold substrate. Therefore, demolding the cast molded product There is no need to add extraneous contaminating additives to the liquid composition for use. Typically, Alkoxylation near the lower end of the above range is important for plastics and rubbers. This method was found to be advantageous for fluid molding of molds.゛ In one example of forming metal containers, particularly aluminum cans, the lubricant has both hydrophilic and oleophilic properties. consisting of an alcohol mixture forming an emulsion with a composition in equilibrium with . For example, such marmagions are water-soluble alcohols containing 20% or more EO. Coxylated Guerbet Approximately 10 to 60% alcohol and oil-soluble alkoxylated gel About 10% to about 40% Guerbet alcohol and about 0% non-alkoxylated Guerbet alcohol It is produced by combining ~20%. This mixture contains mineral oil This provides a system with low viscosity and high rinsability. Ru. If the hydrophilic-to-lipophilic ratio (HLB) is large, the substance is water-soluble. However, small HLB indicates that it is an oil-soluble substance. can be changed to change its solubility in water.

In other examples, the unalkoxylated components in the mixtures described above can be combined into gels of relatively low purity. 50% or less, as in the case of deriving the products of the invention from base alcohols. be able to.

Surprisingly, such impure Guerbet alcohol can be alkoxylated and Excellent washability is achieved when used for subsequent esterification and/or subsequent esterification. Seki A related impurity is the unreacted alcohol in the Guerbet reaction, which necessarily Low molecular weight, e.g. in Guerbet alcohol products and Cannizzaro soap by-products It has half the number of carbon atoms as exists in . These impurities are Up to about 50% by weight, usually up to about 30% by weight when mixed with the alcohol product Can exist in amounts. Therefore, a preferred composition for metalworking is 50% by weight The following preferably contains a small amount of linear low molecular weight alcohol; during the reaction to produce the alkoxylated Guerbet material of the present invention. may be alkoxylated and/or esterified.

Also, emulsions or mixtures of the alkoxylated Guerbet raw materials or mixtures thereof described above may be used. The solution is water, mineral oil, alkoxylated and non-alkoxylated paraffinic compounds. Various solvents and/or suspending agents including compounds, ethers, fatty acid ketones, etc. It can be made using . When making such dilutions, the diluent and product or product mixture in a ratio of about 20=1 to about 1:20, preferably about 10:1. ~ about 1:10.

Typically, the Guerbet products of the present invention are useful when a metal surface comes into contact with another surface to create friction. be sprayed, dipped or otherwise applied in an amount sufficient to provide lubricity to the metal surface. attached to the metal substrate by any convenient method. A specific amount of lubricant must be used. depends on the particular operation and processing temperature. Therefore, for 1 kg of metal A small amount of about 0.0001 g to a relatively large amount of about 3 g of the product of the present invention is can be used. For forming aluminum beverage cans, 1 kg of metal is required. It is relatively common to use from about 0.001 to about 1 g of the product of the invention.

Many advantageous results are achieved by using the products of the invention as lubricants. Ru. This lubricant is highly resistant to oxidation and odor, and is resistant to ambient temperatures. maintain liquidity. Furthermore, such products can be deposited on metal surfaces under forming processing conditions. Shows good substantivity, but can be removed by washing with water. Clean metal surfaces with virtually no oil slick residue or spots that are easily removed Generate a surface. The fact that the product of the invention can be completely removed by washing is This is highly desirable when forming metal containers.

The reason is that the products of the invention leave no degradable residues that later contaminate the whiteness of the container. This is because they do not. These properties can be maintained even by extremely low concentrations of pollutants. Necessary when molding aluminum cans for beverages that are easily contaminated.

The products of the present invention are obtained by alkoxylating the starting material Guerbet Alfur and then It is produced by esterification as required. Guerbet alcohol and The method of manufacturing them is well known and we do not consider it necessary to explain further by way of example. I can do it. The preferred Guerbet alcohol used in the method of the invention is 2-ethyl- Hexan-1-ol, 2-hexyl-eicosan-1-ol, 2-hexyl -Decan-1-ol, 2-octyl-dodecane-1-ol, 2-butyl-o Cutan-1-ol, 2-decyl-decane-1-ol, 2-myristyl-A Cosan-1-ol, 2-cabryl-eicosan-1-ol, 2-coco-cosi 2-coco-cocan-1-ol, 2-crow-octa Decan-1-ol, isocetyl alcohol, 2-hexazosyl-octadecane -1-ol and the like.

These Guerbet alcohols and other Guerbet alcohols have units in the product As the following formula: (In the formula, R, R', x, y and Z are the same as above) the desired amount to produce the corresponding alkoxylated Guerbet alcohol. is alkoxylated by reacting with an alkylene oxide. Guerbet The alkoxylate unit introduced into the molecule is a propylene oxide unit or a propylene oxide unit. Contains a mixture of pyrene oxide units and ethylene oxide units. Alkoxy Rate units are introduced as a mixture for a more random or non-uniform distribution structure or the PO and EO units have a more block-like distribution It can be added in stages. The alkoxylation process ranges from approximately 0℃ to approx. At a temperature of 200°C, preferably from about 110°C to 175°C, about 0.14 kg/cm” absolute pressure (2 psia) ~ approx. 14.06 kg/c+++ absolute pressure (2 psia) 00 psia), preferably about 2.81 kg/cm" absolute pressure <40 psi a) Performed under a pressure of ~4.22 kg/cm” absolute pressure (60 psia). The exothermic reaction of the heat removal efficiency and the addition of PO and/or EO Depending on the amount, the time is from about 4 hours to about 25 hours, more usually from about 5 hours to about 10 hours. E The O:PO ratio is between about O:1 and about 20:1, preferably between about 1=4 and about 4:1. You can change it with As mentioned above, the product can be fully propoxylated. or contain a mixture of ethylene oxide and propylene oxide units. can have If a mixture of alkoxylated units is desired, the gel base The alcohol is first brought into contact with the desired amount of ethylene oxide, then the desired amount of the product. Preferably, it is contacted with pyrene oxide. Then ethoxylation-propochymo The rubberized Guerbet is again contacted with an additional amount of EO to produce a typical block-like structure.

The alkoxylation reaction is carried out under basic conditions, preferably about 0.0 Potassium hydroxide in an amount of 5 to about 0.5% by weight, preferably about 0.1 to about 0.3% by weight. Addition of aluminum, sodium hydroxide, sodium methylate, strontium carbonate, etc. and implement it.

The reaction product can be recovered by distillation and used directly as a lubricant or as a suitable can be converted to the corresponding ester by reacting with a suitable esterifying agent. Ru.

The esterification is carried out at a temperature of from about 1=4 to about 300°C, preferably from 140°C to about 210°C. It is carried out at atmospheric pressure or under a slight vacuum, such as 10 mmh, at temperature. This reaction The treatment is carried out for about 2 hours to about 24 hours, preferably for about 4 hours to about 12 hours. produces an esterified product. Water is produced during the esterification reaction. This water is directly It can be removed by direct distillation or by using a binary azeotrope during the process. It's convenient.

Suitable esterifying agents include, for example, olefinically unsaturated acids, aromatic carboxylic acids, alkali Carboxylic acids with koxy substituents or carboxylic acids substituted with cyclohexene groups These acids include monoacids, dimer acids, and and trimer acids. Specific examples of organic acids that can be used for esterification include Lylic acid, aconitic acid, benzoic acid, toluic acid, xylylic acid, methacrylic acid, Dipic acid, butyric acid, capric acid, caproic acid, cinnamic acid, citraconic acid, citric acid , cresotic acid, elaidic acid, glutaric acid, glycolic acid, lactic acid, livric acid , maleic acid, malonic acid, valmitic acid, phthalic acid, propionic acid, salicylic acid , stearic acid, superic acid, succinic acid, tartaric acid, lylunic acid, oleic acid, pime Phosphoric acid, azelaic acid, sebacic acid, naphthalic acid, trimellitic acid, propane -tricarboxylic acid, ethyldicarboxylic acid and myristic acid and mixtures thereof There are things. When using di- or tri-organic acids, the esterification reaction is can be continued until all or part of the boxyl units have been converted to the corresponding ester. can.

Cyclohexenylic acid used for esterification is expressed by the following formula = (in the formula, n is a number from 1 to 3: n is a number from 0 to 10; R4 is an alkyl group or alkyl group having 1 to 15 carbon atoms; Nyl group, 1p and r each represent a number from 0 to 1).

Examples of such cyclohexene-substituted alkyl or alkenylic acids include: formula: %formula% 6-(hept-1-enyl)-5-pentyl-3-cyclohexyl Sen-1,2-cynonylic acid, 5,6-cyptyl group represented by the following formula 2: 1. 2 ．． 4a, 5. 6.8a-hexahydro-1,2-naphthalene caprylic acid, and the following formula: 1, 2. 3. 4.4a, 5. 6.8a-octahydro-5, There is 6-dimethyl-1,2-naphthalene dipropionic acid. Normal, Propenilua The reaction that produces these cyclic compounds from alcohol is a process that produces both acyclic and monocyclic compounds. and a bicyclic compound. lyric acid and olei in the presence of clay catalyst The compound M reacts with phosphoric acid to form the following formula: 9-nonylidene-10-pentyl-1,18-octadecanedical represented by Produces a mixture with bonic acid.

An example of using a dibasic acid as an esterifying agent is alkoxylated gel base alcohol. For example, the following formula is produced by oxidizing cyclohexanol with nitric acid: :%formula% This is exemplified by the reaction with the compound represented by

In this case, one or both carboxyl groups are esterified with alcohol. Depending on the proportion of acid used in the reaction and the reaction time, mono- or Generate tell. Usually a mixture of such monoesters and diesters is obtained. Ru. Similarly, alkoxylated Guerbet alcohols and tribasic acids, e.g. The following formula is produced by oxidation with acid: The reaction with the compound represented by is monoester, diester or triester, Usually a mixture of these is produced. The reason is that alkoxylated gelbean alcohol Depending on the amount of acid relative to the molecule, 1, 2 or 3 carboxyl groups are esterified This is because it will be done. Other polycarboxylic acids and methods for their production are disclosed in U.S. Patent No. 4.0 75.393: Same No. 4.042.515: Same No. 2.482.761: Same No. 2.793.219; 3.076, 003; and 3.100.7 No. 84. Normally, polycarboxylic acid is manufactured using montmorillonite viscosity. It entails thermal condensation of unsaturated fatty acids in the presence of catalysts such as.

Figure 1 shows the influence of propylene oxide on the compounds of the present invention and the fluidity at low temperatures. Demonstrates ability to hold. In the graph of Figure 1, various alkoxylated The melting point of 2-decyl-decane-1-ol alcohol with the alkoxyl group It was measured based on the total number of moles of converted units. Curve X contains only ethylene oxide. 1 shows alkoxylated Guerbet with Curve Z contains 8066% and PO34%. 1 shows alkoxylated Guerbet with Finally, curve O is 8050% and PO5 The alkoxylated Guerbet containing 0% is shown.

As can be seen by comparing these curves, a total of 8 moles of alkoxylation If the unit is contained in various compounds, it contains 50% of PO. Alkoxylated Guerbet retains fluidity even at temperatures below 0°C; If the same degree of alkoxylation is carried out in a compound containing only , the melting point becomes significantly higher. All of these compounds are normally liquid, but EO alone Alkoxylated Guerbet containing only becomes smaller. The low melting point of the compound indicated by the white lines Z and O is due to this These compounds are desirable because they can be easily incorporated into a variety of formulations. This kind of property is completely unexpected considering the high molecular weight of these compounds. Ru. Therefore, high molecular weight and ease of formulation contribute to excellent lubricity in the same compound. Sato is achieved.

U.S. Pat. No. 4,425,458 describes unalkoxylated gelbearing as a plastic lubricant. The use of colnibasic acid esters is disclosed. However, these Because tel is too lipophilic, it is useful for drawing and ironing metal containers. Not. Moreover, the mechanism of plastic lubrication is also not at all similar to processes involving metal forming. Special Plastic lubrication, as disclosed in the above-mentioned patents and others, It relies on its ability to dissolve in the liquid, i.e. act as an internal lubricant. to this On the other hand, in metal forming, lubricants do not dissolve, but are used on the metal surface to reduce friction. It is applied as a thin film to the surface. The substance of the present invention is poured into plastic. When used as a molding lubricant, the material does not dissolve in the polymer melt. is applied to the surface of the mold in order to quickly demold the molded product. Therefore, the present invention Since the alkoxylated Guerbet products do not introduce foreign materials into the molten mixture, It has many advantages over traditional plastic lubricants.

Having described the present invention generally, the present invention will now be described with reference to the following examples, which are preferred embodiments. explain. These examples are not intended to limit the scope of the invention.

Example 1 Sodium hydroxide was added to 967 g of decyl alcohol in a 2-stand, four-necked glass reaction flask. 30 g of aluminum and 2.0 g of nickel were added with stirring. Add this mixture to 23 Heat to 0 to 250°C and heat for 6 hours while removing water produced by the reaction by distillation. I mixed it up. The reactor contents are then cooled and the product 1-decyl-decane-1 -ol was recovered in greater than 90% yield. Products purified by distillation are Confirmed by liquid partition chromatography (GLC).

The general procedure described above was used in all Examples 2-10 below.

Example 2 Add potassium hydroxide to 510 g of decyl alcohol and 510 g of lauryl alcohol. 20.0 g of aluminum and 1.0 g of zinc were added with good stirring. The generated confusion The mixture was heated to 230-250° C. while distilling off the water produced in the reaction.

The reaction was allowed to proceed, followed by GLC analysis, and the Guerbet alcohol product, 2- Lauryl-decan-1-ol was obtained in greater than 90% yield. Then reaction production The product was distilled to obtain a highly pure Guerbet product.

Example 3 Add potassium hydroxide to 500 g of decyl alcohol and 500 g of octyl alcohol. 30.0 g of aluminum and 2.0 g of nickel were added with good stirring. generate The mixture was heated at 230 to 250°C while removing the water produced by the reaction by distillation. heated to.

The reaction was allowed to proceed, followed by GLC analysis, and the Guerbet-alcohol product, 2 -decyl-octan-1-ol was obtained in greater than 90% yield. The reaction product is Purified by distillation.

Example 4 Octyl alcohol 1000g, potassium carbonate 30.0g and nickel 1.0 g was added while stirring well. The resulting mixture was heated to 220 ml while stirring well. Heated to ~240°C. Water produced in the reaction was distilled off.

The reaction was allowed to proceed and then subjected to GLC analysis. Yield of CI6 Guerbet alcohol was greater than 90%. High purity Guerbet alcohol was obtained by distilling the reaction product. .

Example 5 967 g of isodecyl alcohol and 500 g of tridecyl alcohol were hydroxylated. 30.0g of sodium and copper chromite 2.0 g was added while stirring well.

The resulting mixture was heated to 230 to 25 Heated to 0°C.

Guerbet alcohol product was recovered in greater than 90% yield. Distill the product High purity Guerbet organisms were obtained.

Example 6 1 m (Coco) alcohol (CI2-C4s mixture> Hydroxylated to 967 g 30.0 g of potassium and 2.0 g of nickel were added with good stirring. Living The resulting mixture was heated to 230-250 ml while removing the water produced by the reaction by distillation. heated to ℃.

The % conversion to Guerbet product was greater than 90%. Distill the product to produce C24~ A high purity product consisting of C32 mixed Guerbet alcohol was obtained.

Example 7 Decyl alcohol 967g, potassium hydroxide 30.0g and nickel 2.0g was added while stirring well. The water produced in the reaction is distilled from the resulting mixture. The mixture was heated to 230-250° C. while being removed by.

The reaction was allowed to proceed and then subjected to GLC analysis. 2-decyl-decane-1-ol When the amount reached 60% yield, the reaction mixture was cooled and filtered with Guerbet alcohol. A mixed product containing alcohol and unreacted decyl alcohol was recovered.

Example 8 Add potassium hydroxide to 500 g of decyl alcohol and 500 g of lauryl alcohol. 30.0 g of aluminum powder and 2.0 g of zinc powder were added with good stirring. generate The mixture was heated to 230-250°C while distilling off the water produced in the reaction. .

The reaction was allowed to proceed, followed by GLC analysis, and the yield of Guerbet product reached 75%. Upon reaction, the reaction mixture was cooled and filtered to remove the product 2-lauryl-decane-1-o and unreacted decyl alcohol and lauryl alcohol.

Example 9 Add sodium hydroxide to 500 g of decyl alcohol and 500 g of octyl alcohol. 30.0 g of aluminum and 2.0 g of nickel were added with good stirring. Generate The resulting mixture was heated to 230 to 250°C while distilling off the water produced in the reaction. Ta.

The reaction was allowed to proceed and then subjected to GLC analysis. 2-octyl-decane-1-o When the Guerbet in the alcohol reaches 70%, the reaction mixture is cooled and added with Guerbet alcohol and Collect the product containing unreacted octyl alcohol and desyl alcohol. Ta.

Example 10 To 1000 g of octyl alcohol, 30.0 g of potassium hydroxide and 2 nickel ．． 0 g was added with good stirring. The resulting mixture is mixed with the water produced in the reaction. at 230-250°C while separating it from the refluxing alcohol and removing it from the reaction mixture. heated to. The refluxing alcohol was then recycled to the reactor.

The reaction was allowed to proceed and then subjected to GLC analysis. The yield of CI6 Guerbet alcohol is At 80%, the reaction mixture was cooled and the Guerbet product was removed from the unreacted octyl alcohol. Collected with Cole.

Example 11 A. To 748.5 g of Guerbet alcohol from Example 1, add 2 g of KOH and ethylene oxide. 249 g of oxide was added over 2 hours. An exothermic reaction occurs and the mixture becomes 3. 16 kg/cm at a temperature of 125°C under a pressure of 2 gauge pressure (45 psig) became. The ethoxylated product was stripped under vacuum, then cooled and the product A It was recovered as.

B. To 748.5 g of Guerbet alcohol from Example 2, add 2 g of KOH and ethylene oxide. 500 g of oxide was added over 2 hours.

The resulting exothermic reaction produced a pressure of 3.52 kg/cm (50 ps) ig) and the temperature reached 180°C. ethoxylated product under vacuum) IJ pumped, cooled and collected as Product B.

To 748.5 g of ethoxylated Guerbet alcohol from C0 Example 11A, 2 g of KOH and 250 g of propylene oxide were added over 2 hours. then the same 250 g of ethylene oxide was added over a period of time. by an exothermic reaction The temperature reached approximately 175°C. Ethoxylated polymers with mainly block distribution The lopoxylated-ethoxylated product was stripped under vacuum, cooled and the product C It was recovered as.

D. The operations performed in preparing product B were repeated.

However, if the Guerbet alcohol of Example 1 is used instead of the Guerbet alcohol of Example 2, used. Also, replace 500g of propylene oxide with 500g of ethylene oxide. used for. The resulting propoxylated product was recovered as product.

E, the operations performed in preparing product C were repeated.

However, Guerbet alcohol must first be mixed with 500 g of ethylene oxide and then propylene oxide. Contact with 500 g of ethylene oxide, without final contact with ethylene oxide. It was. Furthermore, the Guerbet alcohol of Example 2 was added to the ethoxylated gel of Example 11A. Used in place of bear alcohol. Exilization with generated block distribution -Propoxylation product was recovered as Product E.

F. To 748.5 g of Guerbet alcohol from Example 1, 2 g of KOH and ethylene oxide were added. A mixture of 250 g of oxide and 250 g of provireon oxide was added over a period of 2 hours. and added. The exothermic reaction brought the temperature to about 170°C. Heterogeneous alkoxylation content The ethoxylated-propoxylated product is stripped under vacuum and cooled. The product was collected as Product F.

The properties of the products A-F described above were evaluated on a scale of 1 (poor) to 5 (excellent). I valued it. The evaluation results were as shown in Table 1 below.

Table 1 BCDEF Volatile’ 123443 Washability’ 234445 Lubricity’ 233443 Liquidity' 214544 1. 24 hours in a 200℃ oven.

2. Wash with 70°F (21.1°C) water.

3. Rothschild friction tester.

4. Value at 20°C.

Ethoxylated alcohol products can be used directly as lubricants or is an alkoxylated alcohol and a C4-C20 organic fat as shown in the examples below. All or part of the ethoxylated alcohol product by reaction with acid It can be converted to the corresponding ester.

Examples 12-18 The amounts of specified alkoxylated Guerbet alcohols shown in Table 2 are added to the amounts shown in Table 2. The fatty acids shown in Table 2 were added.

160-180°C under a pressure of 5 mmHg while distilling water at about 140°C. The esterification reaction was carried out by heating to a temperature of . K with acid value less than 1■/g The reaction continued until OH was reached. By continuously removing water as a by-product High purity esterification product was recovered.

Table 2 12 Caprylic (octanoic) (748,5g) Product B (145 3g) 13 Lauryl (748.5g) Product C (2270g) 14 Stare Phosphorus (748.5g) Product C (1613g) 15 Coco (748.5g> Product D (1690g) 16 caprylic (748, 5g) Product E (155,5g) 17 Dimer acid mixture’ (748,5 g) Product E (238,0g) 18 Dimer acid mixture” (748,5g ) Product E (119,0 g) This compound is a mixture containing M and 0 as described above. Of the alkoxylated Guerbet esters, only Example 12 had a satisfactory flow. It did not exhibit any dynamic properties and did not exhibit excellent lubricity during drawing forming of aluminum cans.

The remaining product has good oxidation resistance and can be easily cleaned from aluminum surfaces. The film obtained by spraying these products onto metal surfaces has excellent lubricity. lum showed good adhesion to metals.

Other dimer acid mixtures, such as those shown in Table 3 below, were used in Example 17 and and in Example 18, it was used instead to have good fluidity and excellent lubricity. The resulting ester was obtained.

Table 3 Tall oil fatty acid 15 70 15 Rilunic acid 5 55 40 Example 19 To 1815 g of the product D of Example 11 in a glass reactor was added the trimester with stirring. 210 g of lithic acid was added. Stir this mixture and evaporate the water. , to a temperature of 170° C. for 6 hours, after which the mixture is cooled, Compounds containing monobasic acids, dibasic acids and acyclic esters of M and O The triester product was collected. The mixed product is KOH with an acid value of less than 1.5 /g Met. The product has excellent metal lubricity, good oxidation resistance and high metal adhesion showed that.

Examples 20-25 The following experiment was conducted using a 0 Schchild friction tester to test the compounds of the present invention and other commercial products. Compounds used commercially, such as Alkalube (trade name) ’) GE-3 (2-decyl-decan-1-ol with 3 EO units); Alcarab GE-5 (2-decyl-decan-1-ol with 5 EO units) and Alcalab G Friction properties for E-20 (2-decyl-decane-1-ol with 20 EO units) were measured and compared. These commercial products were produced in Examples 15.16 and 18. compared to things.

Prepare a 1% solution of the test lubricant in isopropanol in a glass burette. The test was conducted by Stir this solution for 1 hour, then let it stand overnight. Later introduced into Atlab (product name) finish applicator. , apply the solution from the applicator to a 150 denier, 32 fibril polyester The fibers were coated in an amount of 1% by weight, based on the weight of the fibers. coated fibers Pass the isopropanol onto an AI/SS drum at 37.8°C (100’F) was removed and then wound onto an SS spool and kept at a constant temperature of 72°F (22.2°C). and 60% relative humidity for 24 hours. After this equilibration period, The fibers were introduced into a Rothschild friction tester operating at 100-300 m/min. , measured the fiber friction between two transducers. at the fiber-metal interface The coefficient of friction (μm) was recorded and shown in Table 4 below.

Copy and translation of amendment) Submission (Article 184-7, Paragraph 1 of the Patent Act) October 1988 Month 6th ■Ha Director General of the Patent Office Yoshi 1) Takeshi Moon 1. Display of patent application PCT/US8B100278 2. Name of the invention Propoxylated Guerbet Alcohol and Its Esters 3, Patent Applicant Address: Uniin Alps, New Chassis, USA 07470 code 1361 Name: Genf Corporation Representative: Ward Joshua G.I. Nationality: United States of America 4. Deputy manager June 20, 1988 6. List of attached documents Amended scope of claims (wherein R and R1 are each independently an alkyl group having 6 to 15 carbon atoms) represents a group; y represents an integer of 1 to 20; the sum of integers X and 2 is O to 20; R2 is a hydrogen atom, an unsubstituted alkyl group or alkenyl group, or a carboxy aryl group, CUR' group or cyclohexenyl group represented by the following formula: represents alkyl group or alkenyl group, and m represents a number from 1 to 3; n represents any also represents an integer from 0 to 10; p and r each represent a number from 0 to 1; R5 is in each case a hydroxyl group or the following formula: represents an alkoxylated group represented by; R6 has 1 to 10 carbon atoms; (representing an alkenyl group or an alkyl group) Coxylated compounds.

3. The compound according to claim 1, wherein R2 represents a hydrogen atom.

6, R3 is the following formula: 5. The compound according to claim 4, which has a group represented by:

2. A compound according to claim 1 having an iodine number of less than 7.2.

8. The compound according to claim 1, wherein R and R' represent the same thing.

A compound according to claim 1.

12, x, y and/or 2 are all numbers from 1 to 15. Compound.

and the compound according to claim 1 contains the corresponding polyester. A compound according to claim 1.

14. Claim 1, wherein said compound is a mixture of mono-, di- and tri-esters. 3. The compound described in 3.

22, and further the following formula: 21. The set according to claim 20, containing an unalkoxylated Guerbet alcohol represented by A product.

23. said unalkoxylated Guerbet alcohol is present in an amount of about 50% by weight or less 23. The composition according to claim 22.

24. said unalkoxylated Guerbet alcohol is present in an amount of about 30% by weight or less 24. The composition according to claim 23.

25. In producing the alkoxylated compound according to claim 1, (R and R1 in the formula both represent an alkyl group having 6 to 15 carbon atoms. Guerbet alcohol represented by propylene oxide and propylene oxy an alkylene oxide selected from the group consisting of At a molar ratio of alcohol to alkylene oxide of 1:1 to about 1:20, about contact at a temperature of 5°C to about 200°C, Alkoxylate the generated alkoxylation product with an organic acid as required. At a compound to acid weight ratio of about 1=5 to about 5:1 under vacuum, about 1=5 to about 250 A method for producing an alkoxylated compound, characterized by esterification at a temperature of °C.

26. First contact Guerbet alcohol with EO, then contact with PO, and then with X. The sum with y is 1 to 20, and y has a substantially block structure in which y is a number of 1 to 15. Claim 25, wherein the alkoxylated alcohol product of Claim 1 is produced by: the method of.

27. Contacting Guerbet alcohol with a mixture of EO and PO to generate a heterogeneous structure 26. The method of claim 25 for obtaining a product.

28. The method of claim 25, wherein Guerbet alcohol is contacted only with PO.

(wherein R and R1 are each independently an alkyl group having 1 to 20 carbon atoms) represents a group; and the total number of carbon atoms in R+R' is 4 or more, and y is 1 to 20 represents the number; X and 2 are integers, and the sum of X and 2 is 0 to 20; R3 is an unsubstituted alkenyl group, or substituted with a -COOH group or a COR' group represents a substituted alkyl group or a substituted alkenyl group, or R3 is represented by the following formula: represents a cyclohexenyl group, and m represents a number from 1 to 3; n is in either case also represents a number from 0 to 10; p and r both represent a number from 0 to 1, and R5 represents a number from 0 to 1. In both cases, hydroxyl group or the following formula: represents a group represented by R6 is an alkenyl group having 1 to 10 carbon atoms or represents an alkyl group).

36. The compound according to claim 35, wherein x, y and/or 2 represent a number of at least 1. thing.

37, R and R' each represent an alkyl group having 6 to 15 carbon atoms 36. A compound according to claim 35.

38. In a liquid lubricant composition, from about 0.05% to about 1% by weight of claim 35 Compounds listed and water, mineral oil, paraffinic oil, fatty acid ester, fatty acid keto from alkoxylated esters, alkoxylated ketones and mixtures thereof. A liquid characterized by containing a carrier for the compound selected from the group consisting of: Body lubricant composition.

39, further the following formula; (R and R1 in the formula both represent an alkyl group having 1 to 20 carbon atoms. Claim 38 containing unalkoxylated Guerbet alcohol represented by Composition of.

40, for synthesizing the alkoxylated compound according to claim 35 (wherein R and R' is an alkyl group having 1 to 20 carbon atoms) Guerbet alcohol, propylene oxide and propylene oxide and ethylene an alkylene oxide selected from the group consisting of When the molar ratio of ren oxide is 1:1 to about 1:20, the temperature is about 5°C to about 200°C. contacting at a temperature to form an alkoxylated adduct of the Guerbet alcohol; The alkoxylated product is treated with an organic acid having 1 to 20 carbon atoms. At a weight ratio of 1:5 to about 5=1 of rukoxylated alcohol to acid, about esterification at a temperature of 25°C to about 250°C, in which unsubstituted organic acid is used as the organic acid. alkenylcarboxylic acid or -000) or fatty acid substituted with COR' group Aliphatic alkyl carboxylic acids and alkenyl carboxylic acids or represented by the following formula; selected from the group consisting of cyclohexylcarboxylic acids, m represents a number from 1 to 3; n indicates a number from 0 to 10 in each case; r and p are both 0 or the number ma1. 1li4 is an alkyl group or alkenyl group having 1 to 15 carbon atoms. In each case, RS represents a hydroxyl group or the following formula: represents a group represented by; R' is an alkyl group having 1 to 10 carbon atoms or Alkoxyl target characterized by using an organic acid exhibiting an alkenyl group Methods for synthesizing compounds.

41. First, contact Guerbet alcohol with EO, then contact with PO in G), The sum of and y is 1 to 20, and y is a number of 1 to 15. Claim 40 producing the alkoxylated alcohol product of Claim 35 having Method described.

42. Contacting Guerbet alcohol with a mixture of EO and PO to generate a heterogeneous structure 41. The method of claim 40 for obtaining a product.

43. The method of claim 40, wherein Guerbet alcohol is contacted only with PO.

44. Drawing, forging, ironing, rolling, corrugating or canning in processing metal to form a metal container in at least one of the following operations: , in an amount exhibiting sufficient lubrication to reduce friction during operation prior to molding. A method for forming a metal container, comprising bringing the compound described above into contact with the metal.

45, R and R' each represent an alkyl group having 6 to 15 carbon atoms. 45. The method according to claim 44.

46. The method of claim 44, wherein x or y is on average from 1 to about 15.

47. The method of claim 44, wherein the sum of x and z is at least 4.

45. The method of claim 44, wherein 48.2 is at least 1.

international search report 1mM11311IM-^qe-+1+4-9-10PCTzυ5g81002 7ε

Claims (34)

[Claims] 1. The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein R and R1 are each independently an alkyl group having 1 to 20 carbon atoms) group, and the total number of carbon atoms in R+R1 is 4 or more; y is a number from 1 to 20; The sum of integers x and z is 0 to 20; R2 is a hydrogen atom, an alkyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼Indicates a group, and R3 is a hydrogen atom, an unsubstituted Alkyl or alkenyl group, or carboxyl group, COR5 group or formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ or ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ An alkyl group or alkenyl group substituted with a cyclohexyl group represented by and m represents a number from 1 to 3; ko represents an integer from 0 to 10 in both cases. ; p and y each represent a number of 0 to 1; R5 is a hydroxyl group or is the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ an alkoxylated group represented by) Lukoxylated compounds. 2. 2. A compound according to claim 1, wherein x and/or z represent an integer of at least 1. 3. 2. The compound according to claim 1, wherein R2 represents a hydrogen atom. 4. 2. The compound according to claim 1, wherein R2 represents a ▼ group having a mathematical formula, a chemical formula, a table, etc. 5. 5. The compound according to claim 4, wherein R3 represents -hydrogen atom. 6. R3 is the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ 5. The compound according to claim 4, which has a group represented by: 2. A compound according to claim 1 having an iodine number of less than 7.2. 8. 2. The compound according to claim 1, wherein R and R1 represent the same thing. 9. 2. A compound according to claim 1, wherein R and R1 represent saturated groups. 10. Claim 1: R and R1 represent an alkyl group having 2 to 16 carbon atoms. Compounds described. 11. R2 is a mixture of a hydrogen atom and a ▲mathematical formula, chemical formula, table, etc.▼ group. The compound according to claim 1, which exhibits the following. 12. The compound according to claim 1, wherein x, y and/or z are all numbers from 1 to 15. Compound. 13. R2 indicates a group that has a ▲ mathematical formula, chemical formula, table, etc. etc. The ▼ group is obtained from a polybasic acid, and the compound according to claim 1 is 2. A compound according to claim 1 containing a corresponding polyester. 14. Claim 1 wherein said compound is a mixture of mono-, di- and tri-esters. 3. The compound described in 3. 15.6-(hept-1-enyl)-5-bentyl-3-cyclohexene-1, 2. The compound according to claim 1, which is a mixture containing a 2-dinonylic acid ester. 16.5,6-(dibutyl-hexahydro-1,2-naphthalene dicaprylate) 2. A compound according to claim 1, which is a mixture containing stellates. 17.9-nonylidene-10-pentyl-1,18-octadecanedicarboxylic acid 2. A compound according to claim 1, which is a mixture containing an ester. 18. Uralyl ester of ethoxylated-proboxylated-2-decyldecanol 2. The compound according to claim 1, which is 19. Claim 1 which is a cocoester of proboxylated-2-decyldecanol. Compounds listed. 20. from about 0.05% to about 1% by weight in a liquid lubricant composition. and water, mineral oil, paraffinic oil, fatty acid esters, fatty acid ketones. , alkoxylated esters, alkoxylated ketones and mixtures thereof. containing a carrier for said compound selected from the group of A liquid lubricant composition characterized by high resistance to 21. The carrier is a carrier selected from the group consisting of water and mineral oil; The weight ratio of carrier to said alkoxylated compound is from about 20:1 to about 1:20. 21. The composition according to claim 20. 22. Furthermore, the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ 21. The set according to claim 20, containing an unalkoxylated Guerbet alcohol represented by A product. 23. the unalkoxylated Guerbet alcohol is present in an amount up to about 50% by weight; 23. The composition according to claim 22. 24. the unalkoxylated Guerbet alcohol is present in an amount up to about 30% by weight; 24. The composition according to claim 23. 25. In producing the alkoxylated compound according to claim 1, The following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (R and R1 in the formula both represent an alkyl group having 1 to 20 carbon atoms. Guerbet alcohol represented by propylene oxide and propylene oxy alkylene oxide selected from the group consisting of At a molar ratio of alcohol to alkylene oxide of about 1:1 to about 1:20, about 85 ℃~about 200℃, Alkoxylate the generated alkoxylation product with an organic acid as required. from about 125° C. to about 25° C. under vacuum at a weight ratio of compound to acid of about 1:5 to about 5:1. A method for producing an alkoxylated compound characterized by esterification at a temperature of 0°C . 26. Guerbet alcohol is first contacted with EO and then with PO to produce x, z or the sum of x and y is from 1 to 20, and y is a number from 1 to 15. A method for producing an alkoxylated alcohol product according to claim 1 having a structure of The method according to claim 25. 27. Contacting Guerbet alcohol with a mixture of EO and PO to generate a heterogeneous structure 26. The method of claim 25 for obtaining a product. 28. 26. The method of claim 25, wherein Guerbet alcohol is contacted only with PO. 29. The alkoxylated Guerbet alcohol is a C1-C20 aliphatic carboxylic acid, C 1-C20 aromatic carboxylic acid, C1-C20 olefinically unsaturated carboxylic acid and Bi-formula: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ or ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (n and R5 in the formula are the same as those described in claim 1; m is 1 to Represents the number 3; r and p both represent the number 0 or 1; R4 represents 1 to 15 cyclo, which represents an alkyl or alkenyl group having carbon atoms A claim of esterification with one type of organic acid selected from the group consisting of hexenyl organic acids. 25. The method described in 25. 30. 30. A product of the method of claim 29. 31. 26. A product of the method of claim 25. 32. 30. The method of claim 29, wherein the organic acid is a monocarboxylic acid. 33. 30. The method of claim 29, wherein the organic acid is a dicarboxylic acid. 34. 30. The method of claim 29, wherein the organic acid is a tricarboxylic acid.