TW384300B - Process for improving color of basic metal organic salts and stabilizing halogen-containing polymers therewith - Google Patents

Abstract

A light colored basic alkali or alkaline earth metal organic salt is obtained by the reaction of a basic metal compound, an alkyl phenol and/or a carboxylic acid, carbon dioxide, and thereafter post-treating the reaction product with an organic phosphite. Alkaline earth metal salts of phenols and carboxylic acids include barium or calcium. Organic phosphites include trialkyl or dialkyl phosphites such as triisodecyl phosphite or diisooctyl phosphites.

Description

A7 B7

Related patent applications This application is a continuation of the application for a series of provisional patent applications No. 60 / 006,384 filed on November 8, 1995 and No. 60/0 19,719 filed on June 13, 1996. The applications are intact and are incorporated herein by reference. Scope of the invention The present invention is one of methods for producing light-colored, smoke-soluble biochemicals of the phenols and or monocarboxylic acids, and the native metal M, in which various methods are used. Class as a promoter. More specifically, the present invention relates to reacting an alkaline earth metal compound, an alkylphenol and / or a carboxylic acid, and carbon dioxide to produce a reaction product and post-treatment with an organic sulfite A method for improving the color of the reaction product to produce a light-colored alkaline earth metal organic salt. The alkaline alkaline earth metal organic salt of the present invention is used as a stabilizer for a halogen-containing polymer such as polyethylene gas (PVC). BACKGROUND OF THE INVENTION The preparation of printed materials such as polyacids, pit-based powders, and acids that are overbased or similar by the Central Ministry of Economics and Consumer Cooperatives is disclosed in the following U.S. patents: 2,61 6,904 2,760,970; 2,767,164; 2,798,852; 2,802,816; 3,027,325; 3,031,284; 3,342,733; 3,533,975: 3,773,664; and 3,779,922 one. The use of these perovskite metals in triazine-containing organic polymers is described in the following U.S. patents: 4,159,973; 4,252,698; and 3,1-9,823. In recent years, the use of overbased barium in stabilizer formulations has increased during the year. This is due to the fact that overbased barium salts have performance advantages over neutral barium salts. The paper size is subject to the Chinese national standard (CNS > A4 rule, "Grid (210X297 mm). A7 B7. V. Invention Explanation (2) True. The performance advantages related to hyperbarium barium ft are low plate out, excellent color maintenance, good long-term thermal stability, good compatibility of the stabilizer ingredients, and Others. Unfortunately, most of the experimental barium salts are dark-colored, and although these dark-colored, over-exposed barium salts are effective stabilizers for organic polymers containing organic pigments, their dark colors cause the final The discoloration of the product. This property essentially inhibits the use of the experimental barium salt with a dark color in the use of a polymer product that requires a light color. According to the guidance of US Patent No. 4,665,1 17, a light color is prepared. Or pick up earth metals *, where alkane is used as a promoter. However, alkylphenol is also a major cause of color in the final product. ”This problem was overcome by the use of cyclopropane, Phenolic hydroxyl The production of argon and the color-limiting species ", however, has the disadvantages associated with this method, mainly due to the toxic nature of propylene oxide. Propylene oxide is also classified as a possible carcinogen and experimental Laboratory animal absorption studies have shown evidence of a link to cancer. Propylene oxide is also a severe eye irritant, and long-term exposure to propylene oxide vapor can cause permanent damage to the eyes. In addition, propylene oxide is extremely flammable And in some cases naturally explode. The boiling and flash point of propylene oxide at 94 ° F is 200 ° F. Therefore, extreme care is required at the workplace to handle propylene oxide. For propylene oxide Special storage equipment and other safety facilities are necessary "US Patent No. 4,665,117 describes the use of propylene oxide at 150 ° C. At this temperature, propylene oxide will be tied to gas, and the phase will be Λ in Under these operating conditions, since propylene oxide will escape from the reaction mixture, it is necessary to exceed the stoichiometric amount of propylene oxide to complete the reaction. China National Standard (CNS} A4 # (210X297 mm) Please write the note f on the back of this page first to write this page) Equipment-Book the standard of the Ministry of Economic Affairs 扃 Printed by the Consumer Consumer Cooperative A7 B7 Staff of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs Printed by the consumer cooperative V. Invention Description (3) and this requires additional treatment of excess propylene oxide ". Therefore, it has further improvements in the manufacture of metal salts for inspection and for overcoming the problems in the manufacture of ethyl acetate. The need for problems associated with the use of propylene oxide in polymers and other light-colored liquid alkaline earth metal organic salts containing a plain polymer. Summary of the Invention The present invention is directed to improving self-contained A method for preparing a kind of alkaline earth metal organic s prepared by a mixture of hope. For example, the method includes reacting a picky alkaline earth metal compound, an alkylphenol and / or a carboxylic acid, and carbon dioxide to produce a base metal organic salt and a phenol or a phenolic reaction product that produces a color. Ingredients> Thereafter, the base metal salt reaction product is treated with an organic phosphorous acid vinegar to react with the color-producing component and thereby improve its color. Suitable organic phosphites include a variety of diorganyl phosphites and triorgan phosphites. Depending on the specific organic phosphite and the color-producing component, the color improvement reaction can proceed in different ways, as more specifically disclosed below. For example, in one method of the present invention, salty organic phosphites destroy colored species that are made via or in conjunction with phenol. In another form of the method, the salt phosphoric acid phosphite prevents the formation of colored species by reaction with phenol. Although not wishing to be bound by theory or institution, it is believed that this composite pick-up metal salt reaction mixture is used for the reaction of organic phosphites with color-forming phenols or phenols. Product reactions »and thus provide a light-colored Somatic metal organic salts are very unexpected. However, this is organic-β- in the stabilizer composition of fluorinated vinyl resin (please read the note ftf on the back before filling this page) oi binding 'The size of the paper is applicable to China National Standards (CNS) Α4 Terms · (210X297 mm) A7 B7 5. Invention Description (4) Known uses of phosphites. It has many benefits related to the method of the present invention over previous techniques. Organic phosphites are better than propylene oxide Easy and safe to handle. Organic phosphite is a compound with high boiling point and high flash point, while propylene oxide is a low boiling point and very flammable substance. Preferably, the organic phosphite liquid used in the present invention The skeleton can be easily introduced into the reaction system. Moreover, a stoichiometric amount of phosphorus phosphine can be used for the reaction. This is different from the use of epoxide, in which the gas state of propylene oxide is used in · Practically requires an excess of propylene oxide for reaction. In addition, the phosphorous acid ester obtained by the present invention. · The treated metal organic salt is superior to that disclosed in US Patent 4,665,117. Performance advantages of materials such as better compatibility and lower viscosity in stabilizer systems to allow easy handling, storage, and filtration ". Description of preferred embodiments A. Basic methods and important features economic The method of the present invention for improving the color and stability of alkaline alkali or soil test metal 蜃 obtained from a mixture containing a phenol is printed by the Zhunzhan Shellfish Consumer Cooperative, which includes the following stages * (Α) 在A mixture containing at least one soil metal base and at least one alkyl phenol is prepared in the absence of free oxygen, and the ratio of the equivalent of the acid earth metal to the alkyl halide is greater than 1: 1; or, at least one A mixture of an earth metal base, at least one phenol, at least one monocarboxylic acid, and optionally at least one aliphatic alcohol. The ratio of the equivalent weight of the monocarboxylic acid to the phenol is at least about U: 1, and the ratio of the metal to other components. The equivalent ratio of the combination is greater than 1: 1. (B) The mixture is treated with an acidic gas in the absence of free oxygen. The paper scale is applicable to the Chinese National Regulations (CNS) 4 rules (2ι〇χ297). ) Printed by A7 B7__ printed by the Central Government Ministry of Economic Affairs and Consumer Cooperatives. 5. Description of the invention (5) until the titratable alkalinity (phenolphthalein indicator) of the mixture has been substantially reduced, and (C) is used at the end. An organic phosphite that reacts with the color-producing ingredients present in the mixture is treated with a reactive metal organic «reaction mixture. A darker colored product due to the presence of oxygen or an oxidant is therefore best, including the segment (A), The entire method of (B) and (0) is performed in the absence of free oxygen. Generally, the method is performed in an atmosphere of nitrogen. The most important characteristics of the method include stage (0, which is in the Sui paragraph (B)). Finished as an intermediary or reaction product. The manufactured metal-organic ironing appliance has the ability to inhibit and / or destroy the color-generating components or products produced by phenol or phenol-based reaction products in the reactions described above An organic phosphite treatment. If the components that produce color are suppressed and / or destroyed according to the method of the present invention, the product obtained by this method is darker and, after standing, the color is suspected to become darker. When following the method of the present invention, the initial product is pale and does not noticeably darken after standing. Qualified colors according to the ASTM D1 500 standard are at most about 3, preferably about 1 to 2. As stated above, although not wishing to be bound by theory or institution, depending on the color-producing component and the organic phosphite, the color improvement reaction may be performed in different ways. For example, when phenol is present, a trialkyl phosphite, such as triisodecyl phosphite, can react with phenol and form oxygen with hydrogen with higher stability than hydrogen-oxygen bonds through the substitution of phosphorus by hydrogen substitution of phenol. This is a bond that prevents phenol from forming color species in the reaction mixture. As another example • ·., Example, when phenol has reacted to form a phenolic reaction product (which is a color-producing component such as a hydrazone), then a diisooctyl phosphite-8-paper size 14 Use Zhongguan Jiaxian (CNS) A4_ (21GX297mm) ~ Please read who's note on the back of the article &^; write this page) • Binding A7 ___ · _B7 V. Description of the invention (6) Can destroy the phenolic reaction Product with improved color. In either case, the organic phosphite improves color by inhibiting or destroying the color-producing components that can be attributed to phenol or a phenol-based reaction product. b. Sexual metal organica Throughout the scope of this patent specification and the patent application, the term "pickability", as applied to tritium or soil metal organic salts, is used to indicate a metal composition contained in it The ratio of the metal to the organic part is larger than the stoichiometric ratio of the neutral metal salt. That is, the number of metal equivalents is greater than the number of equivalents of the organic part. In some cases, the extent of excess metal found in aging metal salts is stated as a "metal ratio". As used herein, the metal ratio means the ratio of the total amount of alkaline earth metal to the number of equivalents of the organic portion in the oil-soluble composition. In this technique, the picking metal is often called "toad sex" or "transcendent sex" to indicate the presence of excess swilly ingredients. The method of the present invention can be used to prepare a comparison of phenol and / or carboxylic acid. Light coloured test salt. For example, when an alkaline earth metal salt of an alkylphenol and a carboxylic acid is required, the mixture used in the Sui section (A) contains at least one magnetic earth metal, and at least one phenol, at least one monocarboxylic acid, and If necessary, at least one kind of aliphatic moss, the ratio of the equivalent weight of monocarboxylic acid to phenol is at least 1.1: 1, and the ratio of metal f ratio to other components is greater than 1: 1. The mixture used in paragraph (A) of the method of the present invention is prepared and maintained in the absence of free oxygen. Nitrogen atmosphere is preferred. Tritium or earth test alkali is used as a component and can be derived from any earth or test earth metal. The metal alkali derived from the test earth metal is better and its -9-This paper size is applicable to China National Standards (CNS) A4 specification (210X297 mm) Please read the notes on the back first. . Ordered by the Ministry of Economic Affairs, Central Bureau of Standards and Commerce, Consumer Cooperatives, printed A7 B7 V. Description of Invention (7)

Printed by the Central People ’s Government of the People ’s Republic of China, the calcium and barium clams are particularly preferred. Metal hafnium includes metal oxides and argon oxides, and in some cases, sulfides, hydrosulfides, and others. Alkylphenol reactants can be derived from phenol itself or from phenol, or from other polynuclear phenolic compounds. It can also be obtained from a bisphenol such as a bisphenol or the condensation of a ketone with a phenol. Alkyl phenols may contain one or more alkyl groups on the aromatic core, and the number of carbon atoms that must be in the alkyl group is sufficient to produce oil-soluble, overly basic metals * phenols, except for alkaline earth metals and phenols. In addition, the mixture may contain at least one or more monocarboxylic acids. Monocarboxylic acids can be aliphatic. Or aromatic monocarboxylic acids or mixtures thereof. The aliphatic monocarboxylic acids that can be used in the present invention contain an average of at least about 6 atomic atoms and more usually about 6 to about A mixture of about 30 atomic aliphatic singular '9's useful in Sui Duanyu may optionally contain at least one aliphatic alcohol, which acts as a promoter throughout the process. Alcohols useful as accelerators include any of a variety of available substituted or unsubstituted aliphatic or cycloaliphatic alcohols containing from 1 to about 20 or more broken atoms. • Phenols included in mixtures and as needed The amount of yeast as a promoter is not important. The promoter is included in the mixture to facilitate the use of the acid gas during the treatment of the mixture with the acid gas. Generally, at least about 0.01 equivalents and preferably about 0.05 to about 10 equivalents of phenol (and leaven, if present) are used per equivalent of monocarboxylic acid. Larger amounts can be used, for example, up to about 20 to about 25 equivalents of hydrazone and / or phenol, especially in the case of lower molecular weight enzymes and phenols, β water, which can also be present in the mixture if necessary Yangzhong may exist by adding water to the mixture, or water may be "済, leaven", "fishing", or hydrate of earthen calabash, or water chemically combined with metal salts. Other types exist. 10 This paper's rank scale is applicable to the sample rate of the poor countries (CNS) Α% # (210X297 The central standard of the Ministry of Economic Affairs is printed by wc Industry and Consumer Cooperatives A7 _B7 V. Description of the invention (8) In addition to the components described above, use the The reaction mixture for the preparation of pickling metal rhenium will usually contain a diluent β. Generally, any hydrocarbon diluent can be used, and the choice of diluent depends in part on the intended use of the mixture. Most commonly, the hydrocarbon diluent will It is a non-volatile diluent such as various natural and synthetic oils with lubricating viscosity. The amount of picking alkali or earth metal alkali used in the preparation of nylon phenolic phenol is more than 1 equivalent per phenol equivalent. The amount of teaching, and more generally, will be sufficient to provide at least 3 equivalents of metal base per equivalent of alkylphenol. A larger amount can be used to generate more basic compounds and included metals The amount of plutonium can be any amount up to the amount of metal in the product that is no longer effective. When preparing the mixture βί, including the amount of phenol and selected alcohol in the mixture, except for monocarboxylic acids over phenol The ratio of equivalents should be at least about 1.1: 1, which is not important; that is, the monocarboxylic acid is present in excess of phenol. The ratio of the equivalent of the metal base in the mixture and the combination of other ingredients should be greater than 1 : 1, can not supply a basic product. More usually, the equivalent ratio is at least 3: 1. Stage (B) of the method involves treating the above-mentioned mixture with an acidic gas in the absence of oxygen in the absence of oxygen until Using a phenolphthalein to determine the titerable titration "In general, the titerable titer is reduced to less than about 10. In addition to the preferred exclusion of free state oxygen, the first two stages of the method of the present invention do not require Ordinary operating conditions "The ingredients are mixed in the dark section (A), usually heated and then treated with an acid gas, and the mixture can be heated to /, · a temperature sufficient to expel a portion of the water contained in the mixture β mixture is used The treatment of acid gas tt is preferably carried out at an elevated temperature, and for this paper size, the general Chinese National Standard (CNS) A4 specification (2 〖0X297mm） (please read the note f on the back of the special first) < | ^ € This page) Binding and ordering A7 B7 Printed by the Central Consumers ’Association of the Ministry of Economic Affairs, printed by the Consumer Cooperatives V. Invention Description (9) The range of temperatures used in the Sui section can be up to about 200 higher than the weekly temperature Any temperature of * C, and more preferably a temperature of about 75 ° C to about 200eC. Higher temperatures such as 25 ° C can be used, but there is no significant benefit in using such higher temperatures. Generally, A temperature of about 150 eC is satisfactory. The term "acid gas", as used in this patent specification and in the scope of patent applications, is intended to produce a gas of an acid after reaction with water. Therefore Gases such as sulfur dioxide, sulfur trioxide, carbon dioxide, carbon disulfide, hydrogen sulfide, and others are representative of 'acid gases' useful in the method of the present invention. Of these gases, sulphur dioxide and carbon dioxide are preferred, and the most preferred is carbon dioxide. The procedure for preparing alkyl phenols and / or carboxylic acids for picking and picking up metal salts, including the steps (A) and (B) of the present invention, is well known in the art, and the letter is overdone by the procedure The extension of this patent specification is not required. It can be carried out using procedures known in the art and preferably performed in the absence of free oxygen. Examples of patents describing the preparation of basic metal phenates include, for example, U.S. Patent Nos. 2,989,463 and 2,971,014, the patent specifications of which are hereby incorporated by reference. The preparation of ammonium metal salts of monocarboxylic acids using (B) is also well known and a different procedure is described in the prior art, such as in U.S. Patent No. 3,1,94,823 and U.S. No. 3,147,232, which The disclosure of this is hereby incorporated by reference. U.S. Patent No. 4,665,117 is also incorporated herein by reference. C. Organic phosphorous acid overflows the third and important stage in the method of the present invention, including (0 'use has a period of reducing, inhibiting and / or eliminating in the method described above in the stage -12- This paper size applies to the country of China Kneading (Dead Ns) A4 Washing (210X297 mm) (please read "Note f on the back page" first)-Packing. Order from the Ministry of Economic Affairs and Central Government **: Industry and consumer cooperation Du printed A7 B7 V. Description of the invention (10) (A) and at least one organophosphite treatment reaction mixture of phenol or phenol-based anti-beneficial color-producing ingredients. Preferably, the composition obtained in the Sui section (B) Or the reaction product is post-treated with at least one organic phosphite ° Unrestricted 'organic phosphite can generally be characterized by the following formula: R10—P—〇R 2 I' or3 < wherein Ri, R2 and R3 Based on hydrogen, alkyl, alkenyl, aryl, aryl, aryl, and cycloalkyl radicals or radicals, and their substituted derivatives. Therefore, phosphite triesters and phosphite diesters Classes are suitable and include trialkyl or dialkyl phosphites, for example, having about 1 to 18 carbon atoms Alkyl. Specific examples of phosphonium organic phosphites include the preferred liquid tt organic phosphites, tributyl phosphite, triisooctyl phosphite and triisodecyl phosphite, and diisooctyl phosphite. , Dibutyl phosphite and isodecyl 4,4-isopropylidene diphosphite, diphenyl isodecyl phosphite, phenyl neopentyl diferrous phosphite, diphenyl phosphite, Triphenyl Phosphite, Phenyl Diisodecyl Phosphite, and Poly (Isopropyl Glycol Diphenyl Phosphite). Because of this description and illustration, other organic phosphites can be used. Organic phosphorous acid suitable for use in processing The amount of ester is sufficient to inhibit or destroy the color-producing substance. More specifically, the molar ratio of phenol to organic phosphite should be between about 0.5-2: 1, which can be substantially complete. Inhibited or broken, 'Bad substances that produce color. As shown above, these organic phosphites are more than most of the previous techniques -13- (please' read the "note f" page on the back side). Use Chinese National Ladder Standard (CNS) A4 (210X297 mm) Beigong Consumer Cooperative Association A7 B7 5. Inventive (n) methods (such as propylene oxide pits) are easier and safer to handle. Organic phosphites are high boiling point and high flash point compounds, while propylene oxide It is a low boiling point and very flammable substance. Unlike the propylene oxide method, in which the propylene oxide gas "I state, an excess of propylene oxide is required to perform a reaction, and the organic phosphite used in the present invention It is preferably a liquid and can be easily introduced into the reaction system. D. Halogen-containing polymers are most commonly used with the basic metal of the present invention "stable halogen-containing polymer, such as a halogenated ethyl ammonium wax ,-Series of polygas ethylene. It should be understood, however, that the present invention is not limited to one particular southerized vinyl resin such as polyethylene gas or its copolymers. Other resins containing turbid resins including vaporized polyethylene are used and illustrate the principles of the invention , Gas sulfonated polyethylene, gasified polyacetylene, and other types of fluorinated vinyl resins '' fluorinated vinyl resins '', as understood herein, and as perceived in this art, are a common type of Terms and terms are used to define the common monomers (such as ethylene, propylene, vinyl acetate, ethylene fluorene, digas ethylene methacrylate), methyl methacrylate, etc. Esters, acrylates, styrene, and others) derived from the polymerization or copolymerization of these resins or polymers. A simple case is the conversion of gaseous ethylene h2c = chci to synthetic gaseous ethylene (CH2CHC1 di) n, where the halogen is a carbon atom bonded to the carbon chain of the polymer. Other examples of such vinyl resins would include dichloroethylene polymers, gas ethylene-ethylene copolymers, copolymers, polymers, gas ethylene-ethylene copolymers, gas ethylene copolymers , Gas acetam-propylene copolymer, gasified polyethylene, and the like. When • 14 · This paper size is applicable to the Chinese family standard (CNS) Α4 as far as possible (21〇χ ^ 97)-one (please first read the note on the back of this page, and install it on this page), 1T A7 B7 five Explanation of the invention (12) Of course, although other derived compounds such as bromide and fluoride can be used, the derived vinyl chloride is commonly used in the industry. Examples of other halogen-containing polymers include polyethylene bromide , Polyvinyl fluoride, and copolymers thereof. Heat stabilizers for heavy metal compounds derived from vinyl resin compositions are well known. These metal compounds serve during the thermal processing of the halogenated ethylene resin composition to its final shape. Capturing the role of released HC1. Heavy metals can be, for example, lead, cadmium, barium, · or antimony. Stabilizers are usually a metal salt of a carboxylic acid, advantageously a (: 8-(: 24 carbon chain linking single Carboxylic acids such as lauric acid, oleic acid, stearic acid, caprylic acid, or similar fatty acid salts β, and mixed metal salts of these acids, and their preparation are familiar to those skilled in the art related to the present invention. Used ^ including calcium / zinc or barium alone / Zinc admixtures and metal carboxylates in combination with other stabilizers such as betadiones, phosphites and phenolic antioxidants. Metal stabilizers are a mixed metal salt of a carboxylic acid 》 Mixed metal salts of these acids and their preparations are also familiar to those skilled in the art related to the present invention. The following examples are printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to illustrate the method according to the present invention. Preparation of alkaline alkaline earth metal organic salts, but these examples are not considered to limit the scope of the present invention. Unless otherwise stated in the following examples and elsewhere in this patent specification and patent application, all The percentages of ash are by weight and all temperatures are in degrees Celsius. Example 1 Preparation of 165 parts of a commercially available compound containing 12 to 18 carbon atoms of aliphatic yeast, 141 parts of nonanol and 600 parts A mixture of mineral oils, and flushed with nitrogen to remove any oxygen present in the system. Throughout the process

A7 _— _ B7 _ 5. Description of the invention (13) Maintain nitrogen flushing. After a period of 20 minutes, the mixture was heated while stirring to a temperature of about 90T to about 98 * C. At this temperature, 1200 parts of barium hydroxide monohydrate was added incrementally over a period of 30 minutes, and then the temperature of the mixture was raised to about 150-155 ° C, while being removed during the heating period. Any water> Then add oleic acid (258 parts) during the 30-40 minute period while removing the water from the reaction. After adding all the oleic acid ', the mixture was treated with carbon dioxide at a rate of about 2 quasicubic feet per hour (SCFH) for about 4 hours. To reduce the titratability of the mixture. Alkalinity to about 80. Then stop the carbon dioxide feed. While maintaining the nitrogen flush for another 30 minutes to dry the mixture β and then hot filtering (about i25 ° C) the mixture with a filter aid. The filtrate was a dark colored liquid product, which was then treated with diphenyl phosphite (215 parts) and stirred at room temperature for 20-30 minutes. This results in the formation of a light-colored barium organic liquid, which is the desired product with a barium content of 34%. It was found that the ASTM color system was below 1.5. Example 2 The procedure of Example 1 was repeated, except that diisooctyl phosphite (256 parts) was used in the post-treatment stage to replace the diphenyl phosphite, which resulted in a product with essentially the same ASTM color (01 500). Example 3 165 parts of a commercially available mixture of 12 to 1.8 carbon atoms of aliphatic yeast, 141 parts of nonanol and $ 00 parts of a mineral oil. The mixture was flushed with nitrogen to remove the presence in the system Any oxygen. Nitrogen flushing was maintained throughout the method. After a period of 20 minutes, heat the mixture and stir at the same time. -16- This & Zhang scale is applicable to China National Standards (CNS) 8 4 Yongge (210 × 297 mm) ----- „------ ^ I < Please read the note f on the back of the price first and write on this page to order the printing by the Central Ministry of Economic Affairs Central Bureau of Shellfish Consumer Cooperation Du printed Α7 Β7 V. Description of the invention (14)

The central government's bureau of the Ministry of Economic Affairs, the Machining and Consumer Cooperatives, mixes it to a temperature of about 90 eC to about 98 X :. At this temperature, 1200 parts of barium argon oxide monohydrate was added in increments over a period of 30 minutes, and then the temperature of the mixture was raised to about 150-155 eC, while being removed during the heating period. Any water. Oleic acid (258 parts) was then added over a period of 30-40 minutes while removing the resulting water of reaction. After adding all the oleic acid, the mixture was treated with carbon dioxide at a rate of about 2 standard cubic feet per hour for about 4 hours to reduce the titerable titer of the mixture to about 8. The carbon dioxide feed was then stopped while maintaining a nitrogen flush for an additional 30 cents to dry the mixture. The mixture was then cooled to 115-120 * C. Triisodecyl phosphite (TDP) (320 parts) was then added to the reaction mixture. The reaction mixture was then heated at 115-120 eC for 8-10 hours. It was then hot filtered with a filter aid (115-120 ° C), and the filtrate was a desired product with a barium content of 34%. It was found that the ASTM color (0 1 500) was 1. Example 4 The procedure of Example 3 was repeated except that triisodecyl phosphite (170 parts) was used instead of triisodecyl phosphite in the treatment stage following the example, and the ASTM color (1500) was found to be 1. Example 5 In order to show the effectiveness of the heat-determining of the alkaline earth metal organic salt of the present invention, the product treated in Example 3 with phosphorous acid and triisodecyl _ dared to be made into a stabilizer for PVC and marked "hereinafter" "Stabilizer A", as follows: > 17- This paper size is applicable to Chinese National Standards (CNS) A4 Regulation Dream (210 X 297 mm) (please read "Note f on the back side before filling this page")

Ordered by the Central Procurement Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative 384300 a? _______B7 V. Description of the invention (15) Stabilizer A Weight percentage with TDP Example 3 (3 4% over pickability) 25 2 2% Zinc octoate 6.8 Phosphorous acid Diphenyl isodecyl ester 42.4 Dibenzomethane 2.5 Bisphenol A 2 Oleic acid 2 Benzoic acid, 2 Hydrocarbon solvents:-17.3 A 28% overbased barium dodecyl phenol (based on Lubrizol) 2106 for sale) and marked with "Stilbene B", as follows: Stabilizer B weight percentage Lubrizol 2106 (28% peracyl barium dodecyl phenol) 30.4 2 2% zinc octoate 6.8 diphenyl isodecyl phosphite 42.4 diphenyl Methane methane 2.5 Bisphenol A 2 Oleic acid • 2 Benzoic acid-2 hydrocarbon solvents *. 11.9 Stabilizers A and B are each formulated in a standard polyethylene gas compound, prepared with a content of • ^ 2.5 parts , Where the formulations include 100 parts of polyethylene gas (Geon 100 X 450), 30 parts of dioctyl phthalate, and 3 parts of epoxidized-18-This paper size applies Chinese National Standard (CNS} A4 regulations Dream (2 丨 0X297mm) (Please read the note f on the back before filling This page)

384300 V. Description of the invention (16) Soybean oil, 9 parts of titanium dioxide, 10 parts of calcium carbonate and 0.15 part of stearic acid. The PVC formulation was crushed at 350 ° F for 5 minutes, and the static thermal stability was measured at 375 ° F. Within a period of about 68 minutes, when compared with stabilizer B, the stabilizer A of the present invention showed improved thermal stability. Effectiveness, as measured by color change. Therefore, the alkaline earth metal of the present invention, which has been post-treated with an organic phosphite, can be used to replace the currently available metal M with improved properties in color, as measured by a colorimeter, such as An indication of turning yellow. The details of the color 値 obtained through the stabilizers A and B are shown in the table below *. Color B 値 * Time (minutes) Stabilizer A Stabilizer B • 7.5 7.45 7.74 15 9.07 9.83 22.5 12.12 13.3 1 30 18.08 20.49 37.5 18.65 20.76 45 19.4 22.25 52.5 21.32 2 2.99 60 22.07 22.89 68 22.4? 23.05 * This color B That is to say, ASTYE 3 1 3-7 3 is used to measure the above description to provide one of the specific embodiments of the present invention. Reveal the exhibition system, ... It is not intended to limit the purpose of the present invention. If so, the invention is not limited to only the hip embodiments described above. On the contrary, cognition and familiarity with this artisan, in view of -19-this paper size applies the Chinese national standard (CNS) Α4 size (210X297 mm) (please read the note on the back of the page first. $ • m · m ^ i 1. o installation item (Fill in this and buy again) Order-Printed S84300 b by the Consumers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs; 5. The description on the description of the invention (17) will be understood as an alternative and courteous embodiment within the scope of the present invention ^ n. m · mm 1 ^ 1 1 11 ---- n .¾ (Please read the precautions on the back before filling in this page) Ordered by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Shelley Consumer Cooperatives 20 This paper size applies to the Chinese country 橾Mu (CNS) A4 Regulation Dream (210X297 mm)

Claims (1)

Patent No. 85113661 Patent Application Amendment for Chinese Patent Application (88 # a ^ Application for Patent Model Park Central Sample Rate Bureau, Ministry of Economic Affairs, Λ Industrial Consumer Cooperative, Yinjia 1 · A method for improving the color of alkaline alkali metal organic salts or alkaline earth metal organic salts prepared from a mixture containing phenol, comprising: preparing a basic alkali metal organic salt Or alkaline earth metal organic salt and the reaction mixture including the age-producing and color-producing ingredients, wherein the equivalent ratio of the metal salt to the phenol is greater than 1: 1, and treated with carbon dioxide in the absence of free oxygen. The reaction mixture until The titratable alkalinity of the mixture has been reduced, and // the reaction mixture is treated with 5 to 30 parts of organic phosphite per 100 parts of the reaction mixture to react with the color-generating component, thereby improving the basic metal test organic 1 Or the color of alkaline earth metal organic salt ^, the phosphite is selected from the group consisting of tributyl phosphite, triisooctyl phosphite and triisodecyl phosphite, diisooctyl phosphite, dibutyl phosphite and di Tetraisodecyl 4,4-isopropylidene phosphite, diphenyl isodecyl phosphite, phenyl neopentyl glycol phosphite, diphenyl phosphite, triphenyl phosphite Dibenzyl Wine and poly (II-condensing (propylene glycol)) phenyl phosphite. 2. The method according to item 丨 of the application, wherein the organic phosphite is a liquid organic phosphite. 3. The method according to item 丨 of the scope of patent application, wherein the amount of the phosphite is reacted with all the color-generating components present. 4. The method according to item 1 of the scope of the patent application, in which the metal is alkaline earth metal 5. According to the method in item 4 of the scope of the application, the soil metal system is tested or rhyme. 6. The method according to item i of the patent application, wherein the mixture further comprises (Please read "Notes on the back of the book before filling in this summer") Order 384300 g __ _ D8 6. Scope of patent application Single bee sturgeon or aliphatic yeast. 7. The method according to item 6 of the application, wherein the alkaline earth metal calcium 'or barium and the organic phosphite are selected from the group consisting of a dialkyl phosphite and a trialkyl phosphite. 8. The method according to item 7 of the scope of patent application, wherein the phosphite is selected from the group consisting of tributyl phosphite, triisooctyl phosphite, and triisodecyl phosphate 9. The method according to item 7 of patent scope Wherein the phosphite is selected from the group consisting of diisooctyl phosphite and diphenyl phosphite. 10. A vinyl compound tree pond composition comprising an ethylene halide resin and 0.5 to 10 parts of a reaction mixture as defined in item 1 of the patent application, per 100 parts of vinyl halide resin. It is selected from tributyl phosphite, triisooctyl phosphite and triisodecyl phosphite, dioctyl phosphite, dibutyl phosphite, and isodecyl 4,4 · isophosphite. Propylene esters, diphenyl isodecyl phosphite, phenyl neopentyl glycol squinate, diphenyl phosphite, triphenyl phosphite, phenyl diisodecyl phosphite and poly (-Contracture (propylene glycol)) phenyl phosphinic acid is treated with organic linoleic acid. {Please read the note on the back of the page before filling in this page) d. 、 1T The printed paper size of the Central Cooperative Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives is suitable for the countries with difficulty (CNS M4 specification (2 丨 0X297 mm) ) No. 85113661 Patent Application Chinese Patent Amendment Amendment (88 # a ^ Applicant Patent Amusement Park) Central Sample Rate Bureau, Ministry of Economic Affairs, Λ Industrial Consumer Cooperative, Yinjia 1 · A method for improving the color of alkaline alkali metal organic salts or alkaline earth metal organic salts prepared from a mixture containing phenol, comprising: preparing a basic alkali metal organic salt Or alkaline earth metal organic salt and the reaction mixture including the age-producing and color-producing ingredients, wherein the equivalent ratio of the metal salt to the phenol is greater than 1: 1, and treated with carbon dioxide in the absence of free oxygen. The reaction mixture until The titratable alkalinity of the mixture has been reduced, and // the reaction mixture is treated with 5 to 30 parts of organic phosphite per 100 parts of the reaction mixture to react with the color-generating component, thereby improving the basic metal test organic 1 Or the color of alkaline earth metal organic salt ^, the phosphite is selected from the group consisting of tributyl phosphite, triisooctyl phosphite and triisodecyl phosphite, diisooctyl phosphite, dibutyl phosphite and di Tetraisodecyl 4,4-isopropylidene phosphite, diphenyl isodecyl phosphite, phenyl neopentyl glycol phosphite, diphenyl phosphite, triphenyl phosphite Dibenzyl Wine and poly (II-condensing (propylene glycol)) phenyl phosphite. 2. The method according to item 丨 of the application, wherein the organic phosphite is a liquid organic phosphite. 3. The method according to item 丨 of the scope of patent application, wherein the amount of the phosphite is reacted with all the color-generating components present. 4. The method according to item 1 of the scope of the patent application, in which the metal is alkaline earth metal 5. According to the method in item 4 of the scope of the application, the soil metal system is tested or rhyme. 6. The method according to item i of the patent application, wherein the mixture further comprises (Please read "Note $ on the back side before filling in this summer")