TW457237B - Method to produce and purify cyclic esters - Google Patents

Abstract

Methods are provided for the production, recovery and purification of cyclic esters. Such methods include producing a cyclic ester composition containing at least one impurity, contacting the cyclic ester composition with at least one adsorbent to remove the impurity and recovering the purified cyclic esters. Also included are methods of cyclic ester purification involving multiple adsorption operations. The methods of the present invention can produce highly purified cyclic esters. Such compositions are suitable for use in the manufacture of polymers having an average degree of polymerization in excess of about 1700.

Description

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 457237 Α7 Β7 V. Description of the Invention (1) This application is a continuation of US Patent Application No. 08 / 128,797, which was filed on September 29, 1993, and the latter is 1992 US Patent Application No. 07 / 854,559, filed on March 19, 2014, is now a continuation of US Patent No. 5,319, 107, which is incorporated herein by reference for complete reference. The present invention relates to a method for producing, recovering, and purifying cyclic esters and cyclic ester compositions. In a particular embodiment, the present invention relates to the manufacture, recovery and purification of lactide and lactide compositions. Cyclic esters are suitable for a variety of applications. For example, cyclic esters derived from hydroxycarboxylic acids are suitable for the preparation of environmentally biodegradable plastic tree materials, and for plastic phosphine materials, they are reabsorbed when used in medical applications. Particularly useful polymers are those derived from alpha-hydroxycarboxylic acids, such as lactic acid, because they can be degraded by hydrolysis over time under most environmental conditions. The resulting hydroxy acid units (eg, lactic acid) or the oligomers derived therefrom can be easily absorbed by the microorganisms in the environment and converted aerobically to thorium dioxide and water, or anaerobic to carbon dioxide and methane. Cyclic esters, such as cyclic esters of hydroxycarboxylic acids, can be made by a number of mechanisms; however, such cyclic ester products typically contain a variety of undesirable impurities. Such impurities can degrade the cyclic esters in the product, resulting in the resulting cyclic esters having a short shelf life. For example, the free acid and water in the cyclic ester composition can increase the hydrolysis of the cyclic ester bond, degrading the cyclic ester back to the hydroxycarboxylic acid or other degradation products. In addition, impurities in the cyclic ester composition can interfere with the cyclic ester polymerization reaction rate and molecular weight, thereby preventing the formation of a higher molecular weight polymerization product. Therefore, in order to obtain a substantially pure cyclic ester, it is basically free of compounds that would degrade or interfere with subsequent chemical reactions, such as the polymerization of cyclic esters to high molecular weight (please read the precautions on the back before filling this page). h · This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 × 297mm) 1-4 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 457237 A7 _____ B7 V. Description of the invention (2) Polymer, Impurities. Some methods are known for purifying synthetic cyclic ester compositions. Such methods include solvent crystallization, solvent washing, solvent extraction, distillation, melt crystallization, and sublimation. Although satisfactory results can be obtained under controlled laboratory conditions, many methods are difficult to apply to industrial childcare components because they are complex or have unrealistic operating parameters. In addition, such methods may require expensive energy, expensive equipment, or expensive reagents. Furthermore, there may not be mechanical energy to implement these methods on an industrial scale. Other methods are not acceptable industrially because cyclic esters may be degraded to low purity due to dwell time or temperature limitations in the method when performing cyclic ester purification. Furthermore, many methods provide low yields M which are uneconomical. For this reason, inexpensive and reliable methods are needed to purify cyclic esters. In particular, methods are needed to obtain cyclic esters of sufficient purity that can be used to produce high molecular weight polymers. Furthermore, there is a need for a method for purifying some cyclic esters which is capable of recovering all cyclic ester isomers. According to the present invention, there are provided methods for producing, recovering, and purifying cyclic esters in a fluorene ester composition. One aspect of the present invention is a method for making a cyclic ester, which includes providing a feed stream including a linear molecule of a monohydroxycarboxylic acid or its ester, salt, or amidine, and removing water from the feed. A cyclic ester composition is produced and the cyclic ester is contacted with an adsorbent to remove at least one impurity in the cyclic ester composition. The feed stream can contain, for example, XA, where XA contains a compound selected from the group The group includes a monohydroxycarboxylic acid or its ester, salt or amine. The paper size is in accordance with China National Standards (CNS) A4 specification (2! 0X297 mm) (Please read the notes on the back before filling the nest. (This page), Tr 457237 Μ_n? V. Description of the invention (3) (X, ίΐ); a constant bond of X i. One-element + + (X a. A>; a constant ternary molecule of X i A (XaA); Xi A ... Straight_quaternary molecule A); A's ... Straight quaternary molecule (X s W; and its compounds. Ideally, the fluorene ester composition contains less than 2 少于 9ϊ5 (¾¾ ), X, Λ grave should show compounds. Impurities that can be removed from the ring composition include those groups that contain free acid (XM, water and mixtures thereof) The so-produced esters can be recovered, such as by solvent or melt crystallization, spray-dried and beaded, or can be aggregated to form high-resolution polymers. Packing-A further aspect of the present invention is to provide purification. The method of forming an ester compound is to include: contacting an ester composition containing impurities with an adhering agent 1 to remove at least one of the impurities from the cyclone compound. The method also includes the following steps: The composition is in contact with one or more a sorbents > 槿 is removed from the phosphonium ester complex in a matrix. 1. Hibiscus or multi-hybrid 1. Ideally, m ffl sorbents will not degrade 琨 in the present invention Cyclic bridging in the rhenium composition: > The adsorbents useful in the invention are those capable of removing impurities, such as χΛ, ion exchange rhenium, and molecular sieves, which can remove water from the cyclic ester composition. In addition, ideally The rubbish attached can be regenerated * and can be used in multi-vehicle adsorption cycle. Economic Qiu Zhongzhong-Offensive: Sealed off the consumer co-operatives in the humble bureau The invention also purifies the cyclic ester composition, fci includes the method of the invention The derived composition. This cyclic ester composition includes those containing phospholipid and less Si about 2 0 The M product of pb water. The composition of the present invention of the present invention is further controlled, including those containing cyclic esters and thio acids that are less than about 丨 0 丨 mmol / g of fat, but also in the present invention.轺 嘀 is an ester product, which contains less than about 200 _) ρΒ water and less than about 1 〇 窀 equivalent of free acid / 仟 cyclic ester is packaged in-water secret 'gas permeability 芘 ϊ 〇tTP and 9ϋ% Under relative source, it is less than about 0.1 g / 1. 00 paper ruler and medium-sized shovel with fog (K: vs Μ 格格加加加 加) 4 5 7 2 3 7 A7 B7 5 2. Description of the invention (in square inches (24 hours). In an ideal embodiment, such packaging materials include foils laminated with a low density polyethylene film. According to the present invention, there is further provided a process for polymerizing a polymer made by polymerizing a cyclic ester and purifying it according to the method of the present invention. Such processes include polymerizing cyclic esters at temperatures above 150 ° C in less than about 30 hours, and the average degree of polymerization of the resulting polymer is greater than about 1,700. Ideally, the polymerized cyclic ester is lactide, and the final molecular weight (Mω) of the resulting polymer is greater than about 400,000. Figure 1 is a flowchart of one entity of the total cyclic ester production and purification process

(Please read the notes on the back before filling out this page.) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Produced and purified polyester. Such compounds are suitable for use in the manufacture of polymers such as monocyclic esters such as lactide and are suitable for use in the production of polylactic acid. In particular, the present invention relates to the manufacture and purification of cyclic esters that are substantially free of impurities that can degrade the cyclic esters or interfere with the polymerization of polyesters into high molecular weight polymers. The method of the present invention includes manufacturing and purifying a cyclic ester derived from a hydroxycarboxylic acid, a hydroxycarboxylic acid ester, a hydroxycarboxylic acid salt, or ammonium hydroxycarboxylic acid. The term `` derived from '' means that in the reaction for making cyclic esters, these components or products of these components are reactants. They will be derived from any two hydroxycarboxylic acids, their esters, their salts or their amines. The resulting ester is converted into a cyclic diester to form a cyclic ester. The cyclic ester may also be a molecular lactone or a cyclic monoester such as propyl ester. The cyclic ester herein is represented by M XD. XiA means -hydroxycarboxylic acid, hydroxycarboxylic acid Acid ester, hydroxycarboxylic acid salt, or hydroxycarboxylic acid amine. X * A refers to a linear dimer molecule of one XiA molecule. X3A refers to a linear dimer molecule of one XA molecule, and XnA refers to π X0 · A molecules Linear η-polymeric molecules. XA without the numbers below indicates one or more) UA, XaA, X3A, and) UA or a solution containing these species. It must be understood that when X is covered by this paper, the Chinese National Standard (CNS) ) A4 size (210X297 mm) 7 Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 457237 A7 _B7 V. Description of the invention (5) When L is substituted, it means that it is a compound based on lactic acid. For example, LA refers to lactic acid Based mixtures, including UA, UA, UA and UA, and LD means Acid ring dimers> Examples of lactide. The cyclic esters of the present invention include those compounds listed above. Ideal XM species for making cyclic esters include, but are not limited to, the following acids and corresponding esters, salts, or Ammonium: lactic acid, glycolic acid, tartaric acid, mandelic acid, malic acid, 1-hydroxyl-cyclohexane acetic acid, 2-hydroxy-2- (2-tetrahydrofuryl) glycolic acid, 2-hydroxy-2- (2 -Furyl) glycolic acid, 2-hydroxy-2 phenylpropanoic acid, 2-hydroxy-2-methylpropionic acid, 2-hydroxy-2-methylbutanoic acid, 2-hydroxybutanoic acid, 2-hydroxyvaleric acid, 2-hydroxyhexanoic acid, 2-hydroxyoctanoic acid, and mixtures thereof. The specific cyclic ester production process of the present invention is described in detail below. However, this type of production process may be a cyclic ester production method in which a cyclic ester is directly formed from a species A Such as described in U.S. Patent No. 5,319, 107. In addition, other known methods can be used to produce cyclic esters, such as the depolymerization of lower molecular weight linear esters or synthesis by the reaction of alpha-halide salts of osmic acid. Purification of esters-adsorption treatment The present invention includes the removal of impurities from a cyclic ester-containing feed. Such impurities include, for example, water, XA (eg, Acid), gold ions, mineral acids, cyclic ester synthesis catalysts and related catalytic degradation products, and typical fermentation acids and alcohols such as formic acid, acetic acid, propionic acid, butyric acid, ethanol and butanol, all of which are Can contribute to the degradation of cyclic esters or interfere with the polymerization of cyclic esters after M to useful high molecular weight polymers. The feed can also include a solvent * cyclic esters have good solubility in it, but it will not degrade cyclic esters, such as with Cyclic esters work. Such solvents include those that are sized to the Chinese National Standard (CNS) A4 (210 × 297 mm) for this paper size 8 (Please read the precautions on the back before filling out this page). 'Packing-Order 457237 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (6) Solvents used in the manufacture and recovery of cyclic esters are as follows. Examples of such solvents include, but are not limited to, xylene, toluene, benzene, anisole, methyl isobutyl ketone (MIBK >, isopropyl ether, and mixtures thereof). A desirable solvent includes xylene. Undesirable solvents Because it interacts with cyclic esters, it includes alcohols, organic acids, esters and ethers containing alcohols, peroxides and / or acid impurities, ketones, aldehydes and amines having a stable enol form. In the present invention In the purification method of *, the feed is subjected to an adsorption step, in which at least one impurity in the feed is adsorbed from the feed by an adsorbent, thereby condensing and purifying the cyclic ester bonds in the feed. The term " Adsorption w refers to the attraction or interaction between a substance and an adsorbent in the feed stream. Ideally, this attraction or interaction between an impurity and an adsorbent is a non-covalent attraction * It is reversible. This type of attraction, for example, is based on the difference in charge or difference in charge distribution between the adsorbent and the impurity, such as the capture of a molecular species in an ion exchange resin. Included in this definition is the concept of ion exchange, Where charged species are adsorbed There is a reversible exchange on the surface or inside the structure. As discussed in more detail below, in the method of the present invention, the resulting purified solution contains a purified cyclic ester, and then M-post-adsorption treatment, such as recovering the solid form of the cyclic ester or Such as the direct application of cyclic esters by polymerization. Adsorbents suitable for the present invention include ion exchange reagents, molecular sieves, alumina, silica gel, activated carbon, clay, and other adsorbents known in the art. The ideal adsorbent is ions Exchange resins, molecular sieves, silica gels, activated carbon and clays. Particularly ideal sorbents include ion exchange resins and molecular sieves. For a specific method, the choice of a specific sorbent depends on the feed (please read the Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) 8-4 specification (2 丨 0X297 mm) 457237 Α7 Β7 Wang, invention description (the type of impurities attached to the paper. For example, if the quality is a XA Acid is usually removed from the feed by contacting it with a weak or strong anion exchange resin. However, it is desirable to remove, for example, X from the feed For the acid impurity of A, it is desirable to use a weak anion exchange resin. The weak anion exchange resin can obtain an acceptable impurity removal rate, but still allow the resin to be relatively easily regenerated. Examples of suitable industrially existing weak anion exchange resins include Re illy Industries, Inc., Indianapolis, Indiana sells products under the trade names REILLEX® 425 and Rohm and Haas, Philadelphia, Pennsylvania under the trade names AMBERLYST® A-21 ° REILLEX® 425 is poly-4-vinylpyridine cross-linked Macroreticular beads. AMBERLYST® A-21 is a divinylbenzene-styrene based resin with tertiary amine functionality. To remove water and impurities from the feed, the feed can be contacted with an adsorbent. The additive printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is selected from the group consisting of molecular sieves, silica gel, and silica gel. It is molecular sieve. The term "w molecular sieve" as used herein refers to an adsorbent whose structural properties promote the adsorption of impurities, including adsorption of cyclic esters. To remove impurities, amines, it is usually desirable to use a complex resin. To remove salts, it is generally desirable to use a Strong anion exchange resin. 'To remove impurity alcohols, it is usually desirable to use molecular sieves or ion exchange resins. Because this type of adsorbent has a strong affinity for higher polar impurities in the feed, such as XA and water, it is usually desirable to Remove these more polar impurities before the alcohol adsorption treatment in the feed. Removing these more polar impurities allows lower affinity alcohols to be adsorbed on these materials, which does not need to be stronger than in the feed. The polar high-affinity impurities compete to increase the capacity of these alcohol adsorbents.

5 (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 10 457237 A7 B7 Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) Steps of contacting the feed stream with an adsorbent It can be carried out at any suitable temperature that has an acceptable rate of adsorption occurrence. Ideally, the temperature of the feed stream is between about 0¾ and about loo :, more preferably between about 25X3 and about 45 = 0. In an ideal entity of the adsorption process of the present invention, the feed is subjected to a first adsorption M to remove a first impurity, and then subjected to a second adsorption M to remove a second impurity. Selective, allowing for more adsorption steps. The purified cyclic ester-containing feed can then be subjected to a post-adsorption treatment to recover the cyclic ester, as described below. The use of such multiple step adsorption processes is particularly useful in the present invention because they provide the removal of multiple impurities from the feed. For example, performing a first adsorption can remove impurities such as XA from the feed, and a second adsorption can remove water from the feed, or vice versa. A third adsorption can be performed selectively, for example, by removing alcohols. A further fourth adsorption may be performed selectively, for example, M-color filtering to remove color objects if present. In multiple step adsorption, each step can be performed in any desired order. In an ideal entity, a suitable adsorbent for use in the present invention is thermally stable at temperatures above 100 t :, more preferably above about 130 °. The term "thermally stable" refers to the ability of an adsorbent to retain its adsorption capacity when subjected to high temperatures, and to retain impurities when the adsorbent resumes normal adsorption over-temperature. For example, although REILLEX® 425 resin can be used to adsorb impurities at temperatures below about 100¾, it is still thermally stable at temperatures up to 26 °. Therefore, this type of resin is particularly suitable for use in a purification process * where the wax is adsorbed at normal operating temperatures and it can be regenerated by increasing the temperature. , --- s · The ideal adsorbent of the present invention includes the degradation of cyclic esters in the feed. ... (谙 read the note $ on the back before filling this page) Applicable to China National Standard (CNS) A4 specification (210X297 mm) 11 457237 A7 __B7 printed by the Consumer Cooperatives of the Central Office of the Ministry of Economic Affairs of the People's Republic of China 5. Adsorbent for description of invention (9). For example, the method of the present invention is performed with an adsorbent, provided that ideally less than about 25% by weight of the cyclic ester is degraded by contact with the adsorbent, and more preferably less than about 10% by weight. Is less than about 5% by weight. In terms of cyclic ester degradation, an adsorbent such as an ion exchange resin is more preferable than an adsorbent such as alumina. The adsorption step of the present invention can be performed by a variety of instruments, such as fixed adsorbents using packed columns or beds, which are known in the art. Some examples of these types of slats are: moving beds, simulated moving beds, two-column arrangements, and three-column arrangements. In addition, adsorbents that can relax in the feed can also be used, such as forming an adsorbent from the adsorbent material and the feed. Slurry. The adsorption operation of the purification process of the present invention can be carried out in a tidy or continuous mode. However, this plutonium adsorption method is ideal for flail operation. In a further aspect of the invention, the adsorption treatment can include an adsorption treatment-an evaporated solvent stream, which is produced by evaporation before a main crystallization purification process. For example, cyclic esters are known to be purified by a variety of crystallization methods, including solvent crystallization. Prior to a conventional solvent crystallization process, a cyclic ester-containing product stream can additionally include impurities and solvents, which can be concentrated by removing a portion of the solvent by evaporation. In this case, the generated evaporated solvent thus includes a small amount of cyclic esters and impurities. Therefore, in this paper, the evaporated solvent stream can be purified by adsorption treatment, and then the evaporated solvent stream can be reused for other unit operations. For example, the evaporated solvent stream can be subjected to one or more hydrazone adsorption steps, such as an acid adsorption step and a water adsorption step to remove acid and water impurities. The resulting solvent stream includes solvents and residual cyclic esters, which were not removed during the adsorption step. Such a stream can then be used in other operations in the overall recovery process. Example (please read the precautions on the back before filling this page). The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 457237 Α7 Β7 5. Description of the invention (10) For example, such a solvent 澝It can be used as a solvent in the solvent crystallization process of the concentrated cyclic ester composition resulting from the initial evaporation of the solvent. Such crystallization can be a multi-stage recrystallization process. The solvent crystallizes from the solvent. The solvent can be further recycled to other places in the overall recovery and purification of the cyclic ester. For example, such a solvent stream includes impurities and cyclic esters that can be recycled to a one-liquid-liquid phase separation step before the cyclic ester-containing product stream is concentrated. After-effect considerations As mentioned above, after adsorption purification, a variety of post-adsorption treatments can be used to recover cyclic esters into solid or directly polymerized cyclic esters. The recovery process includes, in addition to processes known in the art, a concentration process, a drying process, and further purification. In the recovered solid, the cyclic ester can be recovered by spray-drying the purified feed, and the cyclic ester can be recovered for the M powder shape. Spray drying involves exposing the purified feed in a dry gas, ideally a dry and inert opposite pair of rolls, to drive off the solvent from the purified feed. Typically, spray drying is carried out at elevated temperatures. Spray drying results in a powder that can be packaged and sold and is suitable for applications such as the production of polymeric materials. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). In another post-adsorption process, the purified feed can be concentrated, such as by using an evaporator. For example, the purified feed first passes through an evaporator unit where the solvent is driven off. In an ideal entity, a sufficient amount of solvent is driven off, so the remaining cyclic ester mixture contains between about 1% and about 80% by weight of the solvent, more preferably between about 5% and about 50%, and even more Ideally, it is a solvent between about 15% and about 30%. It must be noted that the solvent removed during concentration can be recycled, for example, to return to other stages in the overall process, including, for example, the paper ruler applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) 13 bucket 57237 Α7 Β7 Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 5. Description of the invention (11) If Xi A is recovered before the production of cyclic esters, it is the regeneration fluid of the acid absorption unit, or it is directly returned to the operation of cyclic ester production, as described in more detail below. Such solvents can also be carried forward for use in post-M recovery or purification operations * such as solvent crystallization. After leaving the evaporator unit, the cyclic ester-containing stream can be cooled before further recovery or purification operations. After shrinking, the concentrated, purified feed can be polymerized directly or dried to the final product. In the entity of the dried concentrated cyclic ester material, the concentrated feed can be selectively further purified before drying. There are many ways to accomplish the drying * such as spray drying the concentrated purified feed as described above. Furthermore, the concentrated cyclic ester can be made into small nine. Making small nine refers to the process of a nine-piece solid material. It includes melting the material, spraying the molten material, and then the drop-shaped material is solidified. Making pellets includes atomizing a melt-purified feed that is substantially solvent-free in a cooled, ideally dry and inert, counter-flowing gas, and solidifies the purified feed. Pellets are typically produced near room temperature. The result of making small nine is to produce beads, which can be packaged and sold, and are suitable for use in the production of materials such as polymers. As noted, further purification of the cyclic esters of Huimu can be performed before drying, such as cooling by solvent crystallization, solvent evaporation crystallization, melting crystallization, distillation, or a combination thereof. All of these processes are listed as active purification steps because the desired cyclic ester species ideally undergoes a phase change and is removed from the impure feed. Conversely * M adsorption-based purifications discussed above are listed as subtractive purification steps * because they remove specific impurities from the impure feed. Although the deducted purification step can reduce the amount of impurities, such as acid, water and alcohol, to a very low level ", but if a positive purification step is not used, it may also be absorbed (please read the note # 1 ^ on the back side first) (This page is written on the page) Binding. 'The paper size of the book is applicable to China National Standards (CNS) Α4 Regulation I (2 〖〇X 297mm） 14 37237 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the Invention (L2) This step attracts other undesired species in the resulting cyclic ester product. For example, amidine residues are commonly found in industrial grade solvents such as xylene, and they cannot be removed by M adsorption treatment. If post-absorption treatments only include evaporation and rust-drying or drying, these scum-like residues will eventually be in the cyclic ester product used for the polymerization reaction. Although this particular contaminant does not necessarily affect the polymerization rate and molecular weight of the results, it may negatively affect the test value and the appearance of the cyclic ester product. Both are important to the product. As another example, obtained from M fermentation-based methods) (A usually contains low levels of undefined contamination, which can also pass through the adsorption purification step. For this reason, it is often desirable to include these in the post-adsorption treatment process. One of the positive purification steps. Before the post-adsorption purification treatment step, there are several advantages to using the adsorption step. For example, in the case of post-adsorption crystallization, larger crystals can be generated because when crystallized in a low impurity solution Crystals usually increase in size. Large crystals are easy to handle, have a lower surface area to body ratio, and are generally more pleasing to potential customers of cyclic ester products. As another example, M adsorption removes XA and X before the positive purification step. Water can be used in post-adsorption treatments at higher temperatures without significantly degrading the cyclic ester product. Therefore, for example, high-temperature treatment steps such as the production of nine and distillation can be used to lower the temperature than in the presence of significant XA and water. Degradation. The degree of increase in high temperature treatment of the front purification type post-adsorption treatment step M is evaluated as follows. In a solid hip, the concentrated feed can solvate Crystal to obtain a purified cake, and then further drying to remove residual solvent. There are many forms of equipment that can be used for solvent cooling and solvent evaporation crystallization. Those skilled in the art can choose a suitable form for specific applications. This paper is also suitable for use Chinese National Standard (CNS) Α4 specification (2Ι0 × 297 mm) (Please read the precautions on the back before filling this page)

457237 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (l3) During the crystallization process * the solvent used for solvent crystallization has some functions. By using a solvent for crystallization, a lower temperature can be used than in the absence of a solvent. In addition, the presence of a solvent can reduce the viscosity of the body, thus making it easier to handle and pump the material and improving heat transfer. Furthermore, the presence of a solvent can produce a relatively pure crystallization process, and when the crystallization process provides a medium containing oligomer impurities such as 14 and \ 1 A. Therefore, when the crystal is later separated from the crystalline mixture, impurities such as 乂 1 纟 and \ 1 纟 oligomers are more likely to be separated from the liquid stream rather than sticking to the crystal. The liquid stream resulting from the separation of the cyclic ester crystals can be further processed, and the cyclic ester can be recovered from the liquid stream. In addition, the liquid stream is treated with M to recycle the oligomers of hA and XM in the liquid. In another entity, the cyclic ester can be further purified by melting crystals. The cyclic ester material is subjected to a temperature sufficient to melt the cyclic ester during a melt crystallization process without the need for a solvent that is substantially transparent. The molten material is then cooled to crystallize a portion of the material. Equipment in several forms is available for melt crystallization. Those skilled in the art can choose the appropriate form for an application. It must be noted that melt crystallization has some special advantages over solvent crystallization processes. For example, because the volume of the material to be processed is significantly reduced in the absence of solvents, the same throughput can be achieved with smaller equipment. It has also been found that larger crystals can be obtained by melting crystals. Due to the higher aspect ratio, larger crystals are usually purer than smaller crystals, thus reducing the surface area of the adhering substance. A further entity of the present invention is when the post-adsorption treatment includes an additional purification step such as crystallization, which is selected from isomers including more than one cyclic ester. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm). ) 16 m- al ^ i ^ 1 ^ 1- n ^ i t --- il ^ n I--«— ^ 1! One eJ (Please read the notes on the back before filling out this page) 4 572 37 Economy Printed by the Central Standards Bureau, Shellfish Consumer Cooperative, A7 B7 V. Description of the Invention (l4) Selective cyclamate. This method involves selecting one isomeric species of the crystalline cyclic ester and recovering that isomeric species. This recovery method is applicable when) (4 is a hand-shaped molecule, so it has the form of ^. For example, lactic acid is a hand-shaped species of XiA. Optical isomers of lactic acid, L-lactic acid and D-lactic acid. As a result, lactide is possible L-LY (a monolactide molecule formed from di-L-lactic acid molecules), D-LD (a monolactide molecule formed from two D-lactic acid molecules), endo-LD (eg, M -Lactide, a lactide molecule produced from a lactic acid molecule and a D-lactic acid molecule), or D, L-LD (— an intermolecular species, including an L-LD molecule and a D- LD molecule). Different species of lactide have different melting points. Endo-LD has the lowest melting point, which is 52.8¾, the melting point of both isomeric pure 0-1 ^ and 1-1 ^ is 98.7 ^, and pure 0, Bu 1 ^ has the highest melting point, which is 128¾. For example, a given 0 molecule of an isomeric species has a higher melting point than other isomeric species can be selectively crystallized during the melting and crystallization process. All cyclic ester mixtures are formed As soon as the melt crystallizes the higher melting species at a temperature higher than the lower melting cyclic ester species, the higher crystalline species can be selected. An isomeric species of a given XD molecule has a higher melting point than other isomeric species, and generally has less solubility in any given solvent. At temperatures above the limit where the dissolution of cyclic ester species with lower melting points is the limit Solvent crystallization can selectively crystallize higher melting point species. Then, when recovering the crystalline hips, for example, by centrifugation, the solid is a high-melting isomer, and the remaining lower melting point is added. Heterogeneous species. The cake crystallized from this may be used as one of the two XD polymerization feeds for the XD polymerization step. The other feed of the XD polymerization step can use various paper sizes to apply Chinese national standards (CNS ) A4 size (2ί297 × 297 mm) 17 (Please read the precautions on the back before filling out this page)-Ze-9

457237 A7 B7 V. Description of the invention (15) The same technology is recovered from the liquid residue generated in the selective crystallization step. Each technology includes, for example, spray drying, nine production, crystallization, distillation, evaporation, or a combination thereof. It must be noted that, as discussed above, selective crystallization cannot achieve 100% selectivity. Therefore, in the example discussed on M, the first crystallized portion may contain lower melting species of residual fi. Also the second recovered portion may contain significant amounts of higher melting species. However, as long as the expected tb for the optical isomers of the polymerization operation is between the isomer content of the difluoride XD product, a simple blending operation can be used to adjust the optical properties of the polymerization operation in the XD feed. The true ratio of isomers. This is obvious > because it is a possible method to control the optical isomers of M XD-based polymers, which controls the physical and degrading properties of many KXD-based polymers. In another entity of the post-adsorption process, cyclic esters can be further purified by distillation. Typically, the middle portion is taken as the product in a full batch steamed process. Another method is to use a standard two-column method to produce the middle portion in a continuous distillation system or to extract the product stream by using a side stream in a one-column method to generate the middle portion. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The products of the distillation method can be directly used for XD polymerization. Alternatively, the product can be spray-dried or pelletized and then stored for later use. When the post-adsorption treatment involves an additional distillation purification step * recovery of the volatile isomers of a further solid cyclic ester of the present invention. For example, the boiling points of L-LD, D-LD and D, L-LD are all very close, so distillation cannot be used to separate these substances. However, the boiling point of M-LD is significantly lower than the boiling points of other isomers, so a distillation system can be designed to produce significantly different isomer content18 (please read the notes on the back before filling out this (Page) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 4 57 Α7 Β7 Printed Invention Notes (is two product copies.) Of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. This represents control 〇Isomer content in the feed of the polymerization unit, so the isomer content in the XD-based polymer is controlled. From the previous discussion, it is clear how to control the main problem in the recovery of cyclic esters. Isomeric content in cyclic ester products of polymerization. One of the main advantages of adsorption treatment is that they are non-stereospecific purification, so the isomer content of the product in the adsorption treatment step is different from that in the feed of the adsorption treatment step. The structure content is the same. All M non-purification-based post-adsorption treatment steps discussed here are also non-stereospecific treatment steps. So, for example, if concentration followed by spray drying As a post-adsorption treatment step, the isomer content of the cyclic ester product is determined by the isomer content of the feed to the adsorption purification step. This result is important because by controlling the proportion of isomers fed to the synthesis reactor XA, or By controlling the degree of racemization in the XD synthesis reactor, including changing the temperature, residence time, the degree of racemization agent added to the reactor, etc., or by controlling the XA feed isomers and The combination of XD synthesis reactor conditions makes it easy to control isomers. The M-purification-based post-adsorption treatment steps discussed here have varying degrees of stereospecificity. M-crystallization-based methods often produce purified The product contains only one or two stereoisomers of cyclic esters. As mentioned earlier, other isomers can be recovered from the liquid residue in the crystallization step. In addition, it can also be used in M crystallography based methods. Blocking mode of operation, in which the entire operation of XD synthesis and recovery is time-sharing among the expected true conformers of the cyclic ester product. M distillation-based methods are generally not as robust as crystallization Specific. For example, the boiling point of M-LD is very close to other isomers, it is possible to design the body of one or two products. The isomerism of a product body is applicable to Chinese national standards (CNS) A4. Specifications (210X297mm) 19 I.— i --- L --- installation ------ order ------ J (Please read the precautions on the back before filling this page) 457237 Central Ministry of Economic Affairs Printed by the Bureau of Consumers of the Standards Bureau A7 B7 Five 'Invention Description (17)-The volume content is basically the same as the content of the isomers entering the adsorption unit. The two product distillates described above can be controlled separately in parallel. Isomeric content of the polymerization reaction line operation. Anti-adhesive repurification of the invention The purification process of the present invention can also include regeneration of the consumed adsorbent, wherein the used adsorbent is treated in order to remove or "desorb" at least a portion of the adsorbed tritium And then use a regenerated adsorbent for adsorption. There are many suitable regeneration technologies, depending on the type of adsorbent used. Regeneration usually involves contacting the sorbent with a fluid (gas, liquid, or supercritical) under conditions that allow the adsorbed impurities to be desorbed from the sorbent into the crossbones. In the case where the impurity to be desorbed from an adsorbent is water, for example, to desorb from a molecular sieve, the step of desorption is a drying process. This type of drying process is accomplished by drying the adsorbent using known techniques. For example, a typical drying process involves removing the adsorbed water with a sorbent and a hot, ideally, an inert gas. Drying can be performed at any suitable temperature. The ideal temperature is between about 175¾ and about 300¾, depending on the type of molecular trim used. Drying can also be selectively performed in a reduced pressure environment to accelerate water release. In the case where the impurity to be desorbed from an adsorbent includes an XA species and / or an XA oligomer, the desorption fluid may be an organic solvent, an aqueous solution, or a warm gas. For example, impurities can be desorbed from the resin using a solvent that is already in the feed. In addition, other solvents that can dissolve luteolin can also be accepted for desorption, including, but not limited to, those related to adsorption treatment as specified in the discussion above. The ideal desorption solvent is Dijia paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 20 II ^ ------------------------------ Order -^ J (Please read the notes on the back before filling out this page) 457237 Employees of the Central Government Bureau of the Ministry of Economic Affairs have cooperated with each other to print A7, B7, and F5, Invention Description (IS) benzene. In a selective entity, the desorption stream can be heated to improve its effect before the adsorbent is contacted. Contacting the heated desorption fluid with the adsorbent can lead to an increase in the temperature of the adsorbent. This in turn leads to a decrease in the adsorption equilibrium, so that M-partially adsorbed XA species will be desorbed from the adsorbent. The amount of XA desorbed by heating is determined by the amount of temperature rise of the adsorbent and the temperature sensitivity of the adsorption equilibrium for a given combination of adsorbent and solution. Typically, a weak adsorbent, such as a weak anion exchange resin, is more sensitive to temperature changes than a strong adsorbent. Other available methods are heating the sorbent. For example, if the adsorbent is contained in a tube with a shell and a tube heat exchanger, the shell may be heated by applying M steam or other heat exchange medium. In this form, a desorption fluid is still required to remove the XA species from the resin, but the amount of desorption fluid required is usually less than the adiabatic heating cycle described in the previous paragraph. The temperature of the regenerated adsorbent typically ranges from about 100 ° C to about 260T. A suitable temperature can be selected so that a desorption rate of accessible sodium is obtained without substantial degradation or loss of adsorption capacity. In the case where the desorption temperature exceeds the boiling point of the desorption carcass, desorption can be performed under pressure. The main advantage of the thermal regeneration method is that no waste is generated, except for the XA species in the solvent of choice. Therefore, the regenerating release stream can be recycled and saved in several places in the cyclic ester synthesis process with little or no additional treatment. However, the thermal regeneration method is quite mild and cannot strongly adsorb the adsorbed species from the resin. These strongly absorbed species typically include metal ions, extender acids, and catalyst degradation products such as sulfonated xylene. After a period of time, the size of this paper applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -91- ------ ,, --------- order ------ J ( Please read the precautions on the back before filling this page) '45.72 37 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (19) These strongly adsorbed species may reduce the XA capacity of the resin to a certain point. Powerful desorption technology. 4 XA species can also be desorbed by chemical regeneration. These methods use more powerful desorption agents than thermal methods. In chemical regeneration, a caustic solution is used to desorb the resin. XA and other strongly adsorbed species. Caustic soda solution can be aqueous alkali solution or caustic alkali that can be dissolved in polar organic solvents, sisters methanol, although chemical methods are more powerful, using them will have some additional difficulties. First, at the end of the desorption cycle > the resin will contain caustic solutions, which must be removed from the resin before the next adsorption cycle. Because these solutions contain caustic, water, and / or alcohols, all these Cyclic ester recovery or poly The process is harmful and requires fairly stringent removal of these species. Secondly, the effluent regenerated from caustic is usually salty and must be treated before being recycled or placed. This processing equipment can be located in XD production and Equipment opened by another component in the purification unit. Or * If the XA feed to the synthesis reactor is derived from the acidification of the fermentation broth, the regenerated effluent can be sent to the fermentation recovery of the acidification step to supply XA and XE ) Integrated production 0 A combination of thermal and chemical regeneration methods can be used. For example, thermal regeneration is used in many regeneration cycles until the adsorption capacity of the resin falls below the expected minimum. Then, the regeneration capacity of the resin is restored by using one or several K-based regeneration cycles. Then, the heat regeneration cycle can be used again until the adsorption capacity drops below the expected function. In another aspect of the present invention, a plurality of guard columns are used in the form of an upstream of the heat-recoverable XA adsorption unit. The purpose of the protective column is to choose from the feed --------- 1 --- 3 Packing-(Please read the precautions on the back before filling this page) Order J_ This paper size is applicable to China Standard (CNS) A4 specification (210X297 mm) 22 457237 A7 B7 V. Description of the invention (20) (Please read the notes on the back before filling this page) The species with strong adsorptive capacity can be absorbed by XA species, Thermally renewable XA adsorption column. This reduces the frequency with which XA columns need to be regenerated using compounds. Another advantage of this method is that because the guard column is chemically regenerated anyway, the thermal stability of the resin used in the guard column is not an important event. Therefore, inexpensive, high-capacity, low-thermal 'stability resins can be used in guard columns. A good candidate for a guard column resin is the aforementioned AMBERLYST® A ~ 21 resin; it is inexpensive and has a capacity six times that of REILLEX® 425, but its high temperature stability limit is only about 75 ° C. In contrast, REILLEX® 425 is more expensive and has a lower capacity, but can be thermally regenerated at temperatures up to 260TC, making this resin a reasonable choice for XA adsorption applications. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The desorption fluid containing desorbed impurities can be recycled for use in other stages of the cyclic ester production and recovery process. The destination of this type of recirculation stream depends on the nature of the desorbed fluid and the mass in it. For example, if the desorbed crossbones is an organic solvent, such as xylene, and although it is an XA species, a small amount of cyclic esters can be produced during the recycling process. Therefore the * recirculation stream can be directed to a cyclic ester production stage before adsorption. For example, as described in more detail below, the cyclic ester production process can include a phase distribution or extraction step after cyclic ester production but before adsorption. By recycling a regenerating stream to such a phase distribution / extraction step, U) the cyclic esters that can be produced in the adsorption purification, and (2) the oligomers and XA acid species can be separated, and for example in the cyclic ester production It is sent to a hydrolysis unit before the process. In the case where the desorption fluid is water, for example, before the cyclic ester production process, the desorption recycle stream can be directly recycled to a hydrolysis unit. In this case, the hydrolysis of the oligomer in the recycle stream can start with water, thus reducing the water. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X297 mm) 457237 A7 B7 V. Description of the invention (21) The volume required for the decomposition unit. In a continuous process, it includes regeneration of the adsorbent. Two or more adsorption columns or beds can be used. In order to be used alternately, the process can be continuously operated. When an adsorption column or bed reaches its capacity, the column or bed is removed from the operation line and transferred to a new regeneration column or bed to perform the adsorption work. The finely-formed products of the present invention A further aspect of the present invention includes a high-purity cyclic ester composition. Such a composition can be manufactured by the method of the present invention. Cyclic ester compositions such as lactide are unstable in the presence of water and acids. In the presence of water, lactide can hydrolyze * to UA, which in turn can hydrolyze to U A. Furthermore, the free acid can catalyze the hydrolysis reaction. Therefore, the cyclic ester composition according to the present invention has only low water and free acid, and thus results in stability of the result, which is highly advantageous when it is transported and stored and extended shelf life. Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In a lactide product, due to the hydrolysis reaction, every 10 PPn of water consumed will lead to an increase of 0.56 milliequivalents of free Acid / kg LD. Typical specifications for industrial lactide are up to 200 ppb water and up to 1 neq free acid / kg LD. Therefore, even in the case of lactide products that initially meet the product specifications, excess water will be present and free acids M will be produced to a higher than acceptable level during subsequent storage and handling. Therefore, it must be known that the current industrial products will not have a long shelf life due to such high-grade water, and the amount of free acid will rise above their stated amount in a relatively short time due to the hydrolysis reaction. The cyclic ester composition provided according to the present invention has a water content of less than 200 parts per million (ppm), more preferably less than about 60 ppm, and most preferably less than about 20 PPm. Furthermore, according to the cyclic ester composition provided by the present invention, the Chinese National Standard (CNS) M specification (2 丨 0 X 297 mm) is applied at the paper scale. -2 4-457237 Α7 Β7 Printed by the Consumer Cooperative. V. Description of the invention (22) The free acid content per gram of cyclic ester is less than 1 milligram Ueq / kg >, more preferably less than about 0.10 meq / kg, and most preferably less than about 0.04 meq / kg. As mentioned above, water and free acids interact in the cyclic ester composition to degrade the cyclic ester. Therefore, the cyclic ester composition included in the present invention has both low water content and low acidity, as identified above. A further aspect of the cyclic ester composition of the present invention includes a packaged fluorene ester product. Since the cyclic ester product contained is extremely sensitive to water, the product is highly impermeable to water. These products are low in water and acid content and are packaged in packages that prevent significant amounts of water from penetrating into the interior of the cyclic ester-containing composition package. In particular, the ethyl ester composition of the present invention is packaged in a package, and its water vapor transmission rate at 100 ° F and 90% relative humidity is less than about 0.1 g / (100 hours *) (24 hours), and more Ideal is less than about O.OlgAlOO in "(24 hours), and the most ideal is less than about O.OOUMIOO 1) ^) (24 hours) 〇 Suitable packaging and packaging for those skilled in the art, can meet the requirements Technology is known. For example, high-quality LDPE foil laminates can have water vapor transmission rates as low as 0.006 g / (100 inM (24 hours) at 100 ° F and 90% relative humidity. Metallized films are also known It has a low water vapor transmission rate. It can be packed with a double-layer bag with a desiccant in between, or it can even be blocked with a higher water vapor, such as a gold container or a glass container. In addition, storage technology, Such as reducing the relative humidity of the outside air exposed to the package, and / or lowering the storage temperature * can further reduce the degradation of the cyclic ester product. Polymer fines further aspects of the present invention include from acceptable polymerization conditions from (谙 Please read the notes on the back before filling this page) Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -2 5-457237 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) Cyclic esters to produce high molecular weight polymers. It is known that under extreme conditions of low polymerization temperature and long polymerization time, cyclic molecular polymers of fluorene molecular weight, such as polylactic acid, can be obtained. However, polymerization reactions within a short period of time at high temperatures have attempted to produce lower molecular weight polymers. It must be acknowledged that impurities in the ester raw material limit the problem of molecular weight in the polymerization conditions expected in the industry. It must also be acknowledged that the cyclic ester raw material reduces the polymerization reaction rate and therefore increases the need for a given conversion. The reaction time of the rate. Furthermore, it must be acknowledged that the degree of mixing that occurs during the polymerization process has a dramatic effect on the reaction rate, and a higher degree of mixing results in a significantly accelerated rate of the polymerization reaction. The cyclic ester composition with high purity can prepare a high molecular weight polymer that meets industrially accepted conditions. In view of the above, the present invention A further aspect includes a method of making a polymer. Others include cyclizing esters at temperatures above about 150 and less than about 30 hours, where the degree of polymerization of the resulting polymerized composition is greater than about 1, where XD is the defined degree of polymerization. Monomer temperature. The temperature in the further carcass of this method can be higher than about 160 ° C, most preferably greater than about 170 ° C: In further entities, the polymerization reaction time is less than about 15 hours, ideally less than about 5 hours, The most ideal time is less than 15 minutes. There are still further entities in the present invention. As a result, the polymerization degree of the polymerized composition is greater than about 2,100, and more preferably greater than about 2,800. In the ideal entity of the polymerization method of the present invention, The cyclic esters to be polymerized include the cyclic ester compositions described above, which can be produced by the purification methods described herein. The polymerization method of the present invention can be used to prepare high molecular weight polymers. For example, this paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling in this guide)

'.-IT 4 5 7 2 3 7 A7 B7 Printing bags of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) In the case where XD is lactide, the molecular weight of the polymer obtained can exceed ^ = 250,000, the more ideal molecular weight is more than Mw = 300,00, and the most ideal molecular weight is more than 1 = 400,000. In the case where XD is tetramethylglycolide, the polymer can be obtained with a molecular weight of more than ^ = 300,000, a more desirable molecular weight is more than Mw = 360,000, and an optimal molecular weight is more than Mu = 480,000. Preparation of phospholipids The above cyclic ester purification method is applicable to the purification of any cyclic ester-containing compounds. Although the main purpose of the method is to purify the cyclic ester-containing composition from the manufacturing process of the cyclic ester, the purification method can also be used to purify the cyclic ester-containing composition from industrial sources. Appropriate cyclic ester manufacturing methods have been disclosed *, for example, in U.S. Patent No. 5,319,107 and pending U.S. queue No. 08 / 128,797, which are incorporated herein by reference. These disclosures provide general cyclic ester manufacturing. An ideal solid skeleton includes making a cyclic ester by providing an XA-containing feed stream * and processing the feed stream to form a cyclic ester directly from component X2 A in XA. In another ideal entity, the cyclic ester manufacturing process includes (1> a feed stream providing component XA in a solvent, and (2> removing water from the feed stream to produce a product stream containing the cyclic ester, Wherein the concentration of X »A and higher oligomers in the product stream is less than about 20% by weight of the reaction mixture in the process. Further desirable methods of making cyclic esters include U) providing a solution containing dilute in an organic solvent The XA feed stream; and (b) removing water from the feed stream, the polyester is produced directly from the) UA. Various cyclic ester production methods can also be included before the adsorption and purification of the above ------------ ^) equipment -------- order ------ J (Please read the note on the back first Please fill in this page for more details.) This paper size is in accordance with China National Standards (CNS) A4 specifications (210X297 mm) 27 457237 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (25) One or more痼 Start the purification step. A first such initial purification step can include the production of a cyclic ester in such a state that, after the reaction mixture is prepared, a two-beta equilibrium liquid phase is formed, which essentially separates 0 from the impurities. One such phase mainly contains XiA and the parent "oligomer. The method includes providing a recovered solvent for the cyclic ester manufacturing mixture, and the recovered solvent can be a solvent used to make the cyclic ester. It must be noted that the second phase may include a The elixir of the second phase, or mainly contains) (4. Then, the adsorption treatment of the cyclic ester M on rhenium is recovered from the first phase. The cyclic ester production mixture can further include a soluble esterification reaction catalyst such as sulfuric acid, which Ideally partitioned into the second phase. In this case, the catalyst is easily separated from the cyclic ester. Any solvent having suitable characteristics according to the functional parameters of the recovered solvent described above can be used in the process of the present invention. More specifically, Applicable recovery solvents include xylene, toluene, anisole, benzene, MIBK, and isopropyl ether. More ideal recovery solvents include xylene and toluene, and xylene is more desirable. O The cyclic ester production mixture is divided into the first The phase separation step from the second phase is typically accomplished simply by cooling the mixture without stopping any mixing or other agitation. In addition, it is possible to use a porous medium or electricity Special equipment to make them agglomerate. These methods can be performed in batches or continuously using standard phase separation equipment known to the skilled person. Phase separation is used to separate the cyclic esters from the "△" and "eight of the oligomers" In addition to the method M of solvent, in another entity, an additional solvent extraction step for the second phase is performed, and the second phase is rich in oligomers of ΑΑ and ίΜ. This solvent extraction step is performed to recover the residual Cyclic esters and solvents in the second phase. For example, I —.------ oi— (Please read the notes on the back before filling out this page) Order i " This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 28 Printed by 57237 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (26) The solvent is a typical recovery solvent, and the second phase is introduced into an extraction unit to be recovered in the first Residual cyclic esters and solvents in the two phases. Other cyclic ester production methods are known and can be applied to the production of the cyclic esters of the present invention. For example, an additional method for making a cyclic ester includes including a portion of a feed stream containing XA Evaporate and reverse In the zone, a part of the feed stream that has been evaporated is activated, and the pressure and temperature conditions maintained in the reaction zone are sufficient to keep the evaporated part in an evaporating state and generate cyclic esters. The manufacture of cyclic compounds can also be achieved through the use of α-methane salts Depolymerization and condensation reaction. For example, a polylactic acid-containing composition can be obtained by depolymerization using the "back loop" mechanism. In an α-halogenated salt reaction, an α-halogenated salt molecule is used. The present invention further includes a general method for the production of cyclic vinegar and purification by adsorption treatment as broadly described above. A variety of methods for making such cyclic esters are also described above. In an ideal entity, this type of overall process includes (1) providing a feed stream containing XA in a solvent, (2) removing water from the feed stream to produce a product stream that includes cyclic esters, and The concentration of medium A and the higher oligomer is less than about 20% by weight of the reaction mixture in the process; and (3) contacting the product stream with a first adsorbent to remove at least one impurity from the product stream, and selecting From free acid, water and mixtures A purified product stream. Referring now to Figure 1 *, a flow chart of an entity of the present invention illustrates a total production and purification process of the cyclic ester lactide of the present invention. In Figure 1, lactone 100 is sent to a hydrolysis unit 102 and is contacted with water 104 and an isomer control agent 106, which are also sent to the hydrolysis unit. Lactic acid ML3 Form A (please read the precautions on the back before filling this page) • Loading · This paper size is applicable to China National Standard (CNS) A4 specification (210X297 revolution) 29-29 5 7237 A7 B7 V. Description of the invention ( 27) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the higher oligomers are hydrolyzed in the hydrolysis unit, Yuan 102, to produce the main UA and LSA feed i08 into the LD reactor 110. The water U2 used from the hydrolysis unit 102 is rinsed out of the system. The lactic acid in the lactic acid feed 108 is fed to the LD reactor 110, combined with a solvent 114 and, if necessary, a catalyst 116, and the latter two are also sent to the LD reactor 110. In the LD reactor 110, lactide is produced by the aforementioned technique. The water removed in the lactide manufacturing reaction can be recycled and used as the water 104 in the element 102 as previously described. Then the propyl alcohol and solvent mixture 11δ prepared in the LD reactor 11 can be sent to a mandarin distribution or extraction process 12〇 < Removal of impurities from the lactide and solvent mixture for Kailuan, (Eg XA and XA oligomers). The XA impurities 112 removed from the lactide, impurities, and solvent mixture can be recycled back to the hydrolysis unit 102. The purified lactide and solvent mixture 124 can withstand a first adsorption 216 to remove at least a portion of XA impurities, including acid impurities, such as by using an anion exchange resin. The lactide and solvent mixture 128 purified from the first adsorption is then passed to a second adsorption 130 to remove water that may still be present in the purified lactide and solvent mixture 128. The purified lactide and solution mixture 132 from the second adsorption can then be concentrated, such as through the use of an evaporation unit 134, in which the solvent 136 is driven off, which can be recycled or combined with additional solvents to form a solvent stream 114 and sent to the propylene. Lactide reactor 110. The concentrated, purified lactide and solvent solution 140 obtained from the evaporation unit 134 can be further purified as described above, or can be used for polymerization of lactide to polylactic acid. The entity as shown in Fig. 1 also shows the regeneration of the adsorbent in the first adsorption 126 and the second adsorption 130. Solvent 142, such as used as LD reactor 110 (Please read the notes on the back before filling this page).

—W This paper size is applicable to China National Standard (CNS) Α4 size (210X297 mm) 30 457237 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) It can be absorbed in the first The container 126 is brought into contact with the adsorbent in order to desorb the impurities on the adsorbent material. As a result, the solvent 144 containing impurities can be used in the phase separation / extraction apparatus 120 as the initial purification of the lactide and solvent mixture 118. The adsorbent used for the second adsorption 130 can also be regenerated by drying to obtain a mixture of water and solvent 146, which can be recycled back to the hydrolysis unit 102 as described above. The following examples and test results are provided for the sake of clarity and are not intended to limit the scope of the invention.钏 1 The following example illustrates the effectiveness of the purification method-entity of the present invention to obtain a purified cyclic ester of a hydroxycarboxylic acid. A sample of 5 g of racemic 2-hydroxyoctanoic acid in Gill Harbor, 0.22 g of Dowex-50 acid form cation exchange resin (as a reaction catalyst), and 195 ml of toluene were added to a three-necked flask and mixed with M—Heating jacket, thermometer, magnetic stirrer, Dean-Stark tube, reflux condenser, and a rubber partition. The mixture was heated to reflux, the temperature was about 116 = 0, and held for about 4S hours. An aliquot of the reaction mixture, M-diazomethane, was derivatized and analyzed by M-gas-layer-fold mass spectrometer (GC-MS). The peaks were identified as: 2-hydroxyoctanoic acid, a linear ester formed from 2 molecules of 2-hydroxyoctanoic acid; meso isomers of the cyclic diesters of 2-hydroxyoctanoic acid; D and L isomer; and an unknown compound with a longer residence time, generally considered to be the product of one or more higher linear esterification reactions. Purification of 璟 醅 (please read the precautions on the back before filling out this page) -Packing--The paper size of the book is applicable to China National Standard (CNS) Α4 size (210X297 mm) 31 457237 Employees of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 printed by the cooperative V. Description of the invention (29) A 300 ml sample of AMBERLYST® A-21 ion exchange resin was used as an adsorbent. The resin was rinsed with propane several times. The resin was placed in a 1-inch diameter column and then washed with a 1: 1 toluene: acetone mixture to replace any starting water remaining in the resin. The cyclic ester reaction mixture M was diluted with acetone to a 1: i toluene: propane mixture and passed through a previously prepared AMBERLYST® A-21 ion exchange resin bed. The effluent was collected and evaporated to dryness. K gas chromatography analysis of solid skull products. Two peaks were found: the meso isomer of the cyclic diester of 2-hydroxyoctanoic acid, and the D and L isomers of the cyclic ester of 2-hydroxyoctanoic acid. Therefore, the purification of the obtained cyclic ester is a non-stereospecific process, and the amount of the recovered cyclic ester mixed isomers conforms to the composition of the isomers that are improved in the adsorption process by K. No linear esterification reaction products of acid and hydroxycarboxylic acid were found. The total amount of solid product obtained was 0.6629 g. The isolated yield was 34% of the theoretical yield on a Moore basis. MJ2. The following example shows the manufacture and purification of a monocyclic cyclic ester in accordance with the present invention, followed by the manufacture of polymers. It also provides a comparison and attempt of two purification methods in polymerization. Glycolate is produced from crude tetramethyldilactide, which is synthesized from 2-hydroxy-2-methylpropionic acid directly in the liquid phase, using m-xylene as a solvent and p-toluenesulfonic acid as a catalyst. The mixture was refluxed and the water was removed in a Dean-Stark tube. 2.1 Purification and polymerization of ethyl ester The crude tetramethyl dilactide was washed with sodium carbonate, neutralized, dried, and then dissolved in propyl ethyl ester. Pass the crude tetramethyldilactide / acetone solution to the paper containing this paper and apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -3 2-------------, -(Please read the note § on the back before filling this page)-,?!-457237 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People ’s Republic of China (5) Invention Notes (30) AMBERLYST® A-21 Ion Resin A column as an adsorbent to remove acid impurities. The effluent from the column < _ > is dry. The resulting solid skull was recrystallized with petroleum ether and dried. A differential scanning calorimeter analysis of the scabbed tetramethyldilactide sample and found a clear melting point starting at 80.9C. The purified tetramethyldilactide was polymerized with a t-butyl lithium oxide catalyst in about 130t! For about 8 hours. The molecular weight of the resulting polymer was determined by permeation chromatography as Mω = 520,000 and M „= 354,000. 2 _ ,. 2 箆 a: f: h is more than 擐 B is purely pure; and 聚会 g K is a crude tetramethyl di The lactide M sodium carbonate was washed, neutralized, and dried. Using isopropanol as a solvent, the crude tetramethyldilactide was dissolved and recrystallized. A sample of the recrystallized material was analyzed by differential scanning calorimeter and it was found that an宽 A wide melting point of 70,0 ° C. 笫 A single attempt to polymerize the purified material using tin octoate as a catalyst failed. No measurable polymerization occurred, and unreacted tetramethyldi was collected after a long reaction time. Lactide. The second attempt to polymerize the purified material was partially successful. Polymerization was carried out at 130Ό $ 1¾ lithium oxide as a catalyst. The molecular weight of the resulting polymer was determined by permeation chromatography as Mw = 17,200, M „= 14,525 . Only 42% of the original monomer was converted into polymer. The low molecular weight and poor conversion of this comparative example indicate that the purity of the tetramethyldilactide recrystallized from the solvent was insufficient to obtain a polymer of high molecular weight. In contrast, the adsorption-based purification method described in Example 2.1 can produce high-purity tetramethyldilactide, and is suitable for producing high-molecular-weight polymers. 2.3 The second l: h age-old sister-in-law. The speckle aggregation application (please read the precautions on the f side before filling out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (2 〇 × 297 mm) 33 457237 Member of the Central Government Bureau of the Ministry of Economic Affairs x Printed by Consumer Cooperatives

A7 B7 Five 'invention description (M) The crude tetramethyldilactide M sodium carbonate was washed, neutralized, dried, and then dissolved in acetone. The crude tetramethyldilactide / acetone solution was passed through a resin bed containing AMBERLYST® A-21 ion exchange resin to remove any remaining acid species. The effluent from the column was evaporated to dryness. The resulting solid was recrystallized from isopropanol and dried. As a result of a differential scanning calorimeter analysis of a sample of tetramethyldilactide, a clear melting point starting at 81.0¾ was found. In the mouth test, K-tert-butyl lithium oxide was used as a catalyst, and the polymerization of purified dimethyl lactide at 1301C failed. After eight hours, there was little evidence of polymerization. Residual isopropanol removal in the purified tetramethyldisulfide was the cause of the polymerization failure. When the dried and purified tetramethyldilactide removed the solvent adhering to the outside of the crystal, it did not remove the solvent trapped inside the crystal. Therefore, Cixin still has a substantial amount of alcohol in the purified material. The apparent melting point of this example indicates that the purity of tetramethyldilactide is comparable to that of Example 2.1. This example shows that even in the adsorption-based method followed by a positive purification step like solvent crystallization, the use of alcohol elixirs for crystallization can introduce alcohol impurities into the cyclic ester composition and cause the polymerization reaction to fail. Example 3 The following example relates to the recovery of the real skull, one of the purification and recovery methods invented by the invention. A mixed isomerized, ester product. A 1025 g sample of mixed xylene, 50 microliters of sulfuric acid, and some boiling debris were placed in a 2000 ml three-necked bottle equipped with a Dean-Stark tube, a condenser tube, and a heating mantle. The contents are heated to reflux, and 50 millimeters of paper size Chinese National Standard (CNS) A4 specifications (210X297 mm) are added. 34-l · .—, --- r --- η, .ά ----- -IT ------ ^ (Please read the precautions on the back before filling out this page) 457237 Α7 Β7 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Machining and Consumer Cooperatives, 5 '• Invention Note (32) liter of lactic acid solution. The lactic acid solution consists of 9 parts of 88% L-lactic acid and 1 part of 88¾ racemic lactic acid. The overall L: D ratio in the original material is 95: 5. The reaction mixture was heated at atmospheric pressure for about 4.5 hours, during which time a total of 15 ml of water was collected in a Dean-Stark tube. The mixture was cooled to room temperature and partitioned. Purification of ethyl esters: 977 grams of a sample in the upper phase containing lactic acid was added to a bottle containing 214 grams of previously azeotropically distilled REIUEX® 425 ion exchange resin as the acid adsorbent and 144 grams of 3A molecular sieve as the water adsorbent Agent, and 50 g of ammonium sulfonate as an adsorbent for the color body. The mixture was stirred for about 4 hours. A sample of the solution was taken out and filtered through a 0.45 #m filter before analysis. High operation liquid chromatography (HPLC) analysis of the solution showed no detectable free acid. The low detection limit of the HPLC method in this application is 2 meq free acid / kg solution. The HPLC results also showed that the L: D: M [; b ratio of the material did not change due to the adsorption treatment. Kar and Fisher titration showed that the treated solution contained 16 -6 ppm water. Warm linings won the second cool product: > Tongshuai Then the treated solution was convoluted and evaporated to dryness to simulate the operation of a spray dryer. The residual cake is a white snow-like powder. Analysis of the cake showed that the ratio of L: D: M isomers: 96.70: 1.04: 2.26, indicating that a portion of the M-dilactide was lost when evaporated. This is not surprising, as M-dilactide has a higher vapor pressure than other isomers. In industrial installations, a simple stripping section can be used to retain the M-dilactide. The high-performance liquid chromatography of the powder shows that the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (2 丨 〇 × 29? Mm) 35-(Please read the precautions on the back before filling out this page)-Packing-1T 457237 A7 ---- B7 -_ Five 'invention description 〇3) (Please read the notes on the back before filling this page) There is no detectable free acid. In this application, the low detection limit of the HPLC method is 9 aeq free acid / kg of dilactide. m 4 The following example illustrates an entity of the adsorbent regeneration method of the present invention. An adsorption instrument consists of four non-embroidered copper tubes of Γ diameter, each about 5 feet long, which are vertically mounted on a trolley and connected in series. Sample valves are installed on the feed line, between the columns, and on the effluent line. REILLEX® 425 was prepared by azeotropic distillation with xylene to remove any water. The four columns were filled with 311.6 grams, 356.4 grams, 370.1 grams, and 352.3 grams of wet resin, with a total bed length of approximately 16 feet. Pump fresh xylene to the instrument to make the air flow out of the system The feed solution at room temperature was pumped through the adsorption apparatus in an upward flow direction of about 45 g / min so that the surface velocity of the upward flow was 0.39 feet / minute. Samples were taken every 5 hours at a 5 値 sample valve and subjected to high-performance liquid chromatography (HPLC) analysis. After the initial xylene was removed from the strip, the fourth column effluent sample showed no detectable free acid until completion of the column. The completion of the fourth column occurred about 270 minutes after the opening solution was fed. The low detection limit of the HPLC method in this application is 2 tneq free acid / kg solution. The purified stream taken from the fourth column before completion held a sample of 807 grams. To the retained sample was added 178 grams of a 3A molecular sieve sample. The remaining samples were then stirred and stored as M and used. At about 270 minutes and M, the acid components completed on the fourth column had opposite molecular weights. This observation indicates that when the bond length of the linear lactate is increased, the resin capacity 36 1 'paper size is applicable to the Chinese national standard (< 3 Yang) 8 4 specifications (210' 乂: 297 mm) 457237 A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the local shellfish consumer cooperative V. Description of the invention_ (34) The amount is reduced. Feeding was stopped about 480 minutes after the start of the feeding solution, and it was observed that the resin was near full saturation. Sight and front: > Yak Take out the resin from the first column and place it in a three-necked flask equipped with a heating jacket and a condenser. Add sufficient xylene M to cover the resin and heat the mixture until it boils at about 1331. After about a few minutes of boiling, the resin was filtered while hot. In the same case, the resin was boiled a second time in xylene, filtered * and then loaded back into the column. This thermal regeneration process is repeated for the second, third and fourth columns. Fresh xylene was then pumped into the instrument and air was allowed to flow out of the system.筮 Secondary attachment A second room temperature adsorption cycle was performed using the same xylene / lactic acid / lactide solution used in the first adsorption cycle. The flow rate of the second adsorption cycle was about 47 g / min, which resulted in an upward surface velocity of 0.41 ft / min. Samples were taken every half hour and analyzed by HPLC. After the initial xylene was replaced from the system, the sample from the fourth column effluent until the effluent from the column was completed showed no detectable amount of free acid. Completion of the fourth column occurred about 240 minutes after the start of the feed solution. As in the first absorption cycle, the low detection limit for HPLC analysis in this application is 2 meq free acid / kg solution. Before completion of the fourth column, a retention sample of 2,580 grams of purified stream was taken from it. To the retained sample, 570 grams of a 3A molecular sieve sample was added. The samples were then mixed and stored for use after K. Because (1) the first adsorption cycle is carried out until the wax is nearly completely saturated, and (2) the time before the completion of the second adsorption cycle is about the same as the first adsorption cycle, depending on the thermal regeneration of the resin is basically completed .

1 '--- ί ---- ο_ Install-(Please read the notes on the back before filling this page)

This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 37-457237 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (35 will be from the first adsorption and second adsorption cycle The secondary retention sample was combined at 70T; and in a partial vacuum, the material was swirled to remove a portion of the xylene. After the swirled evaporation, the residue was cooled to room temperature, during which time a white needle was formed in the residue bottle. L-lactide crystals. The crystals were filtered, K was washed with fresh xylene dried with 3A molecular sieve, and then dried in a 351: vacuum oven. The free acid cost of the crystalline product was lower than that of the potassium methoxide titration method. Test limit * In this application is 0.02 meg of free acid. Example 5 The following comparative example shows the use of a purified cyclic ester obtained from a 1M entity according to the preparation and purification method of the present invention to make a high molecular polymer, and The molecular weights obtained from the commercially available cyclic esters were used for comparison. The first two tubes of the adsorption apparatus described in Example 4 were equipped with MBEILLEX © 425. M was azeotropically distilled with xylene beforehand. Prepare REILLEX® 425. The third and fourth tubes are filled with 3A molecular sieve beads. Xylene is pumped into the system, the molecular sieve is degassed * and the air flows out of the column. A sample of lactide was dissolved in 4 liters of xylene. L-lactide is a commercial grade, which is believed to be prepared based on the M depolymerization reaction. Before making the solution, the lactide is exposed to the air for a long period of time Make it absorb water and form free acid. The initial lactide contains 91 meg free acid / kg lactide as measured by potassium methoxyl titration. Karl Fisher titrates initial lactide, initial xylene and Lactide-xylene solution, 260, 78 ppm, and 84 ppm of water were obtained. This paper size is applicable to China National Standard (CNS) A4 specifications (2 丨 ox297 mm> 38 ------- ^- --0 ya install ------- order ------- (please read the notes on the back before filling this page) 457237 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Note (36) The crude lactide-xylene solution at a rate of 46 g / min is pumped through the adsorption apparatus. When the original xylene is replaced from the system, the fourth A 4 liter retention sample was collected in the effluent. HPLC analysis of the retention sample showed no measurable free acid. In this application, the low detection limit of the HPLC method was 2 meg of free acid / kg solution. Karl Fisher titrated the retention sample 7.7 ppm of water was shown. Noodles were recovered at 65C and in a partial vacuum by rotary evaporation to retain a portion of the xylene removed from the sample. After the rotary evaporation, the residue was cooled to room temperature > white needles were then formed in the residue bottle L-lactone in crystals. The crystals were filtered, washed with fresh xylene dried with 3A molecular sieves, and then dried in a 35t: vacuum oven. The amount of free acid in the crystalline product was determined by potassium methoxide titration, which was 0.04 aeg, free-acid / kg lactide. The crystalline product of KKarl Fisher titration showed 49 ppm of water. Polymerization of cyclic esters. Six glass tubes were filled with 10 grams each of which was either adsorbed and purified lactide, industrial lactide, or the starting lactide material. Potassium methoxyl Karl Fjsher titration. Industrial lactide contains 1.1 meg of free lactase # 59ρρπι water. To each tube was added 24wl of a 10% (by weight) solution of stannous octoate in dimethyl ether, which corresponds to a catalyst amount of 80 叩 mol or a monomer to catalyst ratio of 12,500: 1. The glass tube is heated to polymerize the contents. The molecular weights shown below are determined by gel permeation chromatography: (Please read the precautions on the reverse side before filling out this page) This paper size is applicable to the Chinese National Standard (CMS) A4 (2Ι〇 × 297 mm) 39 457237 A7 B7 Five 'invention description (37) All materials ΤΠ) Li Xiao Bin 399,800 Ha 255,325 1 Purified lactide 167 4 2 Industrial lactide 167 4 268,700 130,135 3 Starting lactide 167 4 15,100 11,668 4 Purified lactide 145 44.5 441,100 179,600 5 Industrial lactide 145 44.5 196,400 94,200 6 Purified lactide 145 44.5 30,200 29,900 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs because it is derived from purified lactide_ The molecular weight of the polymer is thinner than that of the polymer derived from the starting material. The purification process was successful. The molecular weight of the polymer from purified lactide is from 50-125% compared to 髙. Because the polymerization conditions are the same for H, the difference in molecular weight is due to the purity of the monomer (lactide). Example fi The following illustrates another entity of the purification method of the present invention. Preparation of an adsorbent 100 ml of dry AMBERLYST® A- The 21 resin was placed in a 1-inch diameter glass column. Rinse twice with 100 ral portions of acetone, and then rinse once with K 100 ml of 50% water / 50% acetone. The pH of the first acetone rinse solution is 9, and A yellow color indicates that impurities were removed from the resin during this treatment. Magnesium sulfate (15 g) and 40 ml of 3A molecular sieve were added to the top of the column. Impurities ^ Attach 10 g of L-lactide, 5 g of anhydrous lactic acid, 2 grams of polylactic acid and about 0.5 grams of distilled water were mixed with about 20 ml of acetone and added to a column containing the adsorbent prepared as described above. The lactide produced was eluted from the column. The portion eluted from the column was placed Into a rotary evaporator, gently heat to remove the solvent. Residual propylene 1 .--------, i-- (Please read the precautions on the back before filling this page) Order i spicy_ This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm 40 4572 Sheyin Chlorine A7 B7 V. Description of the invention (38) The further evaporation of the ketone is to place this part in an oven of phosphorus pentoxide. After the residual acetone is removed, the residue is a very white and light flake. The obtained acrylic The yield of lactide is about 93.5%. M 7 The following example shows the improved shelf life and stability of a packaged cyclic ester product of the present invention. A 5 kg lactide sample was placed in a 4 mil thick low density In a polyethylene (LDPE) bag, its water vapor transmission rate is about 0.39 g / (100in2 · 24hr), and another 5 kg lactide sample is placed in an LDPE-foil bag. The vapor transmission rate is approximately 0.0006 g ^ 100in * * 24hr >. The surface area of both bags is 418 square inches, and then two bags of lactide are stored at 100TF and a relative humidity of about 90 炻 for 6 months. Measured at 4 mil Thick LDPE bag of lactide free acid was found to rise to 3332 meg free acid per kg of lactide due to water passing through the LDPE bag, and the amount of lactide free acid in the LDPE-foil bag was found. The rise due to leech penetration is only about 5.4 meg free acid / kg lactide. The various entities of the present invention have been described in detail. It is obvious that these improvements can be made and adopted in substance. However, it is also clear that such improvements and uses are within the scope of the present invention, as proposed in the patent application. This paper standard applies to the Chinese National Standard (CNS) Μ specifications (2) 0 X 297 mm) ih ^ --- install -------- order ------ ^ (谙 Please read the precautions on the back before filling in this page) -41-

Claims (1)

ί 1;.: Printed AS B8 C8 D8 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs VI. Application for Patent Scope No. 84112588 Patent Reexamination Case Application for Amendment of Patent Scope Amendment Date: July 1990 1. A method for manufacturing and purifying cyclic esters, It includes the following steps: (a) providing a feed stream containing XA in a solvent, wherein χΑ system comprises a compound selected from the group consisting of a monohydroxycarboxylic acid or an ester thereof, Salt or amidine (XA); a χιΑ linear binary molecule (X2A); — ^ [eight straight linear ternary molecule (X3A); — and eight straight linear quaternary molecule (χ4Α); — X丨 A linear five-membered molecule (X5A); and mixtures thereof; (b) forming a product stream containing the cyclic ester, wherein the cyclic ester is formed by a method selected from the group consisting of: The method includes removing water from the feed stream to form a product stream including the cyclic ester, where the agronomy of X5A and the higher polymer in the product stream is less than about 2 during the process. 0% by weight; depolymerization reaction; 0:-condensation reaction of self-substituted salt; A gas phase method; and (c) contacting the product stream with a first adsorbent to remove at least one impurity 'selected from the group consisting of free acid, water, and mixtures thereof from the product stream to form a purified A product stream and contacting the product stream with a second adsorbent to remove at least one impurity selected from the group consisting of free acid, water, and mixtures thereof, wherein the product stream includes less than 200 ppm of water 'and the product The stream includes free acid in an amount of less than about 1.0 meq / kg of cyclic ester, and wherein the first and second adsorbents are selected from ion exchange resins and molecular sieves. The paper size applies Chinese National Standard (CNS) A4. Specifications (210 X 297 mm)---- fill -------- I-i I ------- 1-(Please read the precautions on the back before filling this page) -42 457237 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, AS B8, C8, D8. 2. The method according to claim 1 of the patent scope, wherein the -adsorbent will not degrade the ring. 3. The method according to item 1 of the patent application range, wherein the temperature of the product stream in the contacting step is from about 0 ° C to about 100 ° C. 4. The method according to item 丄 of the patent application scope, wherein the temperature of the product stream in the contacting step is from about 25 ° c to about 45 °. (: >> 5) The method according to item (1) of the scope of the patent application, which includes a further step of polymerizing the cyclone in the purified product crO β 6. The method according to item (1) of the scope of patent application, wherein the χιΑ is A compound selected from the group consisting of lactic acid, glycolic acid, tartaric acid, mandelic acid, malic acid, 丨 -hydroxy 丨 _cyclohexyl chloride · § *, 2-meryl group_2- (2-tetra-argon), acetic acid, 2-meryl-2- (2_flam) acetic acid 2-hydroxy_2methylbutanoic acid, 2-hydroxybutanoic acid, 2-hydroxyvaleric acid, 2-hydroxy Caproic acid, acids, salts, esters, or amidines of 2-hydroxyoctanoic acid, and mixtures thereof. 7. A method according to item 范围 of the scope of the patent application, wherein the free acid contains XA. 8. According to item χ of the scope of patent application The method, wherein the first adsorbent comprises an anion exchange resin. 9. The method according to item 8 of the scope of patent application, wherein the anion exchange resin comprises a resin selected from poly-4-vinylpyridine-based resin and The material of the ethnic group consisting of diethylbenzene-benzene-based resin. 10. According to the patent application The method of item 8 'wherein the paper size of the anion exchange is applicable to the Chinese storehouse standard (CNS) A4 specification (210 X 297 mm) • J--1 -------- installed! --- 丨 order ----- 1 --- Line (please read the precautions on the back before filling this page) • 43 · α57237 AS B8 CS DS Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs An anion exchange resin that is thermally stable at a temperature higher than about 10 (rc is a thermally stable anion.) The method according to item 丄 of the scope of patent application includes a further step of regenerating the ~~ adsorbent. The scope is called the method, which further includes the following steps: contacting the product stream with the regenerated first adsorbent to remove at least one member selected from the group consisting of free acid, water and mixtures thereof from the product stream Impurities to form a purified product stream. 13. A method according to item u of the scope of the patent application, wherein the step of regenerating the first adsorbent includes drying the adsorbent. H. A method according to item i of the scope of patent application Wherein the step of regenerating the first adsorbent Including desorbing the impurities from the adsorbent to form a desorbed impurity stream. 15. The method according to item 14 of the scope of patent application, wherein the step of regenerating the first adsorbent includes the adsorbent and a fluid at a temperature From about 0. 0. ^ to about 260 ° C. 16_ The method according to item 15 of the scope of patent application, wherein the fluid includes an organic solvent 'which is selected from the group consisting of xylene, toluene, benzene, benzyl Ethylene, isobutyl ketone, isopropyl ether, and mixtures thereof. 17. A method according to item 15 of the scope of the patent application, wherein the fluid includes deionized water. 18. The method according to item 15 of the scope of patent application, which comprises adjusting the temperature of the first adsorbent to a temperature below about 100. < 3 another step. 19. The method according to item 14 of the scope of patent application, in which the impurity includes the scale of the scale and is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297). --- -44-I 11Ϊ ------ i — — — — I — f Please read the notes on the back before filling in this page) 457237 Printed by A8 BS C8 D8 of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Six 'Patent Application Scope XA. 20. The method according to item 9 of the patent application scope, comprising a further step of recycling the desorbed impurity stream to the feed stream. 21. The method according to claim 19, wherein the desorbed impurity stream further comprises water, and the method further includes a step of hydrolyzing at least a portion of XA in the desorbed impurity stream. 22. The method according to item 1 of the patent application scope, wherein the first adsorbent includes an anion exchange resin to remove free acids, and wherein the second adsorbent includes a molecular sieve to remove water to form a purified product stream. 23. A method according to item 22 of the scope of patent application, including the further step of spray drying the cyclic ester in the product stream. 24. The method according to item 22 of the scope of patent application, further comprising the steps of: evaporating at least a portion of the solvent in the product stream to form a shrunken product stream, and by selecting from the group consisting of spray drying and forming One of the groups of pills to deal with this product stream. 25_ The method according to item 22 of the scope of patent application, comprising a further step of filtering the dehydrated and purified product stream. 26. The method according to item 22 of the scope of patent application, which comprises a further step of evaporating at least a portion of the solvent in the purified product stream to form a concentrated purified product stream. 27. The method according to item 26 of the claimed patent, which involves introducing the evaporated solution into the feed stream to make another step. 28. The method according to item 26 of the scope of patent application, which further comprises polymerizing the cyclic ester in the concentrated, purified product stream. The paper size of this paper applies the Chinese national standard ficNS) A4 specification (210: 297 public love II- II t II — — — If ---- III ^ — ίΛΛ (Please read the notes on the back before filling in this page) -45- 457237 Α8 Β8 C8 D8 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Scope 29. The method according to item 1 of the patent application includes the following steps: this step includes the following steps: before the step of contacting the product stream with an adsorbent, evaporating at least a portion of the solvent from the product stream to produce — Evaporated solvent stream and a concentrated product stream. 30. The method according to item 29 of the scope of the patent application, including the step of further introducing the evaporated solvent stream into the feed stream. The method of item 1, further comprising the steps of: evaporating at least a portion of the solvent from the purified product stream to form an evaporated solvent stream and a concentrated, purified product stream. 32. 依The method of claim 31 further includes the step of introducing the evaporated solvent stream into the feed stream. 33. The method of claim 31, wherein the concentrated, purified product stream includes about 50% to about 80% by weight of cyclic vinegar and the method includes a step of further solution polymerizing the cyclic ester. 34. The method according to item 31 of the claimed patent scope, wherein the concentrated, purified product stream includes greater than about 95% by weight of cyclic ester, and the method includes the step of further melting and polymerizing the cyclic ester. 35. The method according to item 31 of the scope of patent application, which claims that the concentrated, purified product stream includes greater than about 50% by weight Cyclic ester, and the method includes the step of further spray-drying the cyclic ester. 36. The method according to item 31 of the patent application scope, wherein the concentrated, purified product stream includes greater than about 95% by weight of the cyclic ester ' And the method includes the step of further pelletizing the cyclic ester. The paper size is applicable to China National Standard (CNS) A4 specifications < 210 X 297 ----- ~ ------- iyM ------ --Order --------- line- ^ ". ( Matters to read the back of the note and then fill in this page) -46--