TW200815497A - Process for production of high molecular weight polyhydroxy acid - Google Patents

Abstract

There is disclosed a process for producing a high molecular weight polyhydroxy acid comprising the steps of: (a) condensating a hydroxy acid with a functionalizing agent, said functionalizing agent being selected to form a polyhydroxy acid prepolymer having at least three terminal hydroxyl groups thereon after said condensating; and (b) polymerizing said pre-polymer in the presence of a coupling agent under conditions to form said high molecular weight polyhydroxy acid.

Description

200815497 25304pif IX. Description of the Invention: Field of the Invention The present invention relates generally to a method for producing a high molecular weight polyhydroxy acid. The invention is also directed to a system for implementing the method. : [Prior Art] Due to the chemical, mechanical, and physical properties of polyhydroxy acids, it is a very useful material. In recent years, since polyhydroxy acids can be degraded into carbon dioxide and water by microorganisms under natural conditions, the economic importance of polyhydroxy acids is increasing due to their biodegradability. Polyhydroxy acids, such as polylactic acid, have been woven into fibers using the conventional melt-spinning process. It is also easy to prepare spunbound and melt-blown non-woven fibers from polylactic acid (1101>~(^1^1^. These materials can be used in various applications such as household and industrial wipes, diapers). , feminine hygiene products, disposable garments, and anti-UV fabrics. In addition, because polylactic acid is bioabsorbable and is digested by bio〇l〇gical system, it can be easily used in bone or Implants in soft tissue and for resorbable sutures are used in certain applications (such as medical implants, clothing, body, electric brain subjects, and other related components). a polyhydroxy acid whisker having a high molecular weight of at least 5 峨. (4) to indicate a specific mechanical = a mechanical strength. A method for producing a polycarboxylic acid, including The reaction of the machine 200815497 25304pif / glutinous oxime in the compound and in the absence of water in substantial form, the aliphatic monohydroxycarboxylic acid (aliphatic m〇n〇_hydr() xy carboxylic acid) is dehydrated by a condensation reaction. To obtain at least about 5 〇, (10) A polyhydroxycarboxylic acid having a weight average molecular weight. However, this method relies on the use of an organic solvent which may be harmful to the environment. In addition, the organic solvent must be removed from the final polymer to increase the processing cost. Ο ο A method for producing a high molecular weight polylactic acid comprising ring-opening polymerization of lactide using a stannous octoate catalyst. However, the method comprises forming a lactic acid vinegar from an oligocondensate of lactic acid. Prior to the high molecular weight polylactic acid, the mirror was used to separate and purify, which increased the manufacturing cost. The problem associated with some known methods is that the purification step is complicated and therefore because it requires the use of multi-unit operations (ie steaming) Guta, evaporator, miscellaneous converter, pump, etc., in order to separate from the cyclic dimers (such as lactic acid and its filaments). And operate at high temperatures, so the capital, operation and maintenance of the corpse is large. It is possible to reduce the number of distillation steps, however, this will make the recovery rate significantly lower, thereby reducing the yield, and with The economic cost of the post-coating process. The synthesis of the multi-prepared base acid of the middle-aged knives includes the polycondensation dehydration reagent and the water of the hydrazine product. The produced water will become the inhibition synthesis of the polymerization reaction, and it is difficult to be effective and substantial. The removal from the reactant polymer. Known steps, the process has proposed a complex water removal step (water removal such as continuous distillation of water and cyclic dimerization 200815497 25304pif body). However, the equipment used in these methods is inefficiently designed and has resulted in loss of feed product and cyclic dimer. It is therefore desirable to provide a process for making high molecular weight polyhydroxy acids that overcomes or at least ameliorates one or more of the above disadvantages. Further, it is also desirable to provide a system for making high molecular weight polyhydroxy acids to overcome or at least ameliorate one or more of the above disadvantages. SUMMARY OF THE INVENTION According to a first aspect, a method for producing a high molecular weight polyhydroxy acid is provided, comprising the steps of: (a) condensing a hydroxy acid with a functionalizing agent, and selecting a functionalizing agent Forming a polyperacid prepolymer having a terminal hydroxyl groups on the second after condensation; and (b) forming a pre-t-form in the formation of a south molecular weight poly-based group The polymerization is carried out in the presence of a coupling agent under acidic conditions. In a consistent application, the coupling agent is an isocyanate coupling agent. Advantageously, the polyhydroxy acid prepolymer having at least three terminal hydroxyl groups thereon allows for the formation of high molecular weight polyhydroxy acids in the above polymerization step. Advantageously, less isocyanate coupling agent is used per base acid prepolymer relative to the prepolymer having less than three terminal hydroxyl groups, σ having up to two ends without base. According to a second aspect, there is provided the use of a polybasic acid prepolymer having at least three terminal groups for the manufacture of a high molecular weight polyhydroxy acid, the use comprising the steps of: 7 200815497 25304pif (a) in forming a polymeric filament The prepolymer is polymerized under acid conditions. According to a second aspect, there is provided a Southern molecular weight polybasic acid comprising: 1 k: (1) Μ condensing a hydroxy acid with a functionalizing agent, the functionalizing agent is selected to be condensed, formed thereon to have at least Three terminal hydroxyl groups

And 艰 I 〇 (b) The polymerization is carried out in the presence of a coupling agent under conditions in which the chloroform is mashed into a high molecular weight chloroform. According to a fourth aspect, there is provided a reactor (react〇r) having a reaction zone 'this reaction zone containing a polyhydroxy acid prepolymer having at least three terminal hydroxyl groups and a polymerization monomer of a coupling agent A polymerizing monomeric mixture wherein the reaction zone is operated under conditions which form a high molecular weight polybasic acid from a mixture of polymerized monomers. [Comprehensive mode] μ Definition G The following terms and terms used herein shall have the meanings indicated: The term "Southern molecular weight polybasic acid" means having a molecular weight greater than 10 , Q, (10) 〇, preferably greater than 150,000. Polybasic acid. In some embodiments, the polyhydroxy acid has a high molecular weight of from about 100,000 to about 450,000. The term "hydroxy acid," as used herein, means a carboxylic acid in which one or more hydrogen atoms of an aliphatic group or an aromatic group are replaced by a hydroxy group. The term "polycarboxylic acid" as used herein. A polymer that repeats a transbasic acid monomer unit. 200815497 25304pif The term "aliphatic hydroxycarboxylic acid" generally refers to an acid having an alcoholic hydroxyl group and a carboxyl group in the molecule, such as lactic acid, glycolic acid. (glycolic acid), malic acid, tartaric acid, citric acid, hydroacrylic acid, α-hydroxybutyric acid, glyceric acid ), tartronic acid and similar aliphatic hydroxycarboxylic acids. Ο u The term "functionalizing agent" in the context of the present specification is broadly understood to include the ability to carry out a condensation reaction with a hydroxy acid (condensati〇n reacti〇). n) forming any compound having at least two terminal via-based prepolymers. The functionalizing agent may comprise at least one polyol and optionally at least one of polycarboxylic acid and diol (di〇i) Or a combination of a lottery. " ' 立 ^ 醇 醇 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意 意Branched, aromatic lysine) pentaerythritol, tripentaerythritol, glycerol, glycerol (and/or other poly-: alcohol oxime = and cyclic condensation products (such as diglycerin, triglycerin, open and hexaglycerol; Diglycidyl ether, diglycidyl/, pentaglycerol glycidyl ether, glycerol diglycidyl ether, butane H diethylene glycol di-, tris(tetra)ylpropanyl m-glycol, glycidol 1,2,4,5· Cyclohexane tetramethanol, (tetra)alkanol, tetradecyl alcohol, alcohol, 1,5,8-triolol, yiyiyuan triol, guang 3,5-heptan 4,3,5- Glycerol, 2,4,6-heptatriol, 4,4•2, which is a heptyl alcohol, earth, 2,3'pentane, three 9 200815497 25304pif alcohol, 1,1,3- Cyclohexane trimethyl alcohol, U4·cycloheptane triol, cyclopropane triol, 1,2,3-cyclopropane trimethanol, hydrazine, 2,3-cyclobutane triol, 1,2,4-cyclobutane :!:triol, 1,2,3,4-cyclobutanetetraol, hi dimercapto-yi' cyclobutanetetraol 1-by-cyclobutane sterol,][,2,3-pentanetriol, U4-pentanetriol, 2,3,4-pentanetriol, 1,2,3-cyclopentane III Alcohol, iota, 2,3-hexanetriol, 1,2,4-hexane triol, 1,2,3,4-hexanetetraol, cyclohexanetriol, 1,2,5-ring Hexanetriol, 1,2,3, 'cyclohexanetetraol, 12,3,5-cyclohexanetetraol, inositol, and mixtures thereof. The term polycarboxylic acid "includes all acids having more than one buffer. Exemplary, non-limiting examples of polyacids include citric acid (ie, 2-hydroxy-1,2,3-propane tridecanoic acid), 1 , 2,3-propane tricarboxylic acid, i, 2,3,4-butane tetradecanoic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid (ie, 2, 2匕oxybis(succinic acid)), thiosuccinic acid, anti-small succinic acid, all cis_1,2,3,4-cyclopentanetetracarboxylic acid, mellitic acid, alkylene Cycloalkyl tricarboxylic acid, trimethyl-cyclohexane tricarboxylic acid, U.5-trimethylidene+3,^cyclohexamethylene dicarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,2, 3,4_butadienic acid, 1,2,3,4,5,6-cyclohexanehexanic acid, cycloalkyltricarboxylic acid, cycloalkyltetracarboxylic acid, cycloalkylpentanoic acid, ring Alkyl hexacarboxylic acid and mixtures thereof. As used herein, the term "diol" refers to all molecules having at least two alcohol functional groups thereon. Exemplary non-limiting diols include saturated and unsaturated alkyl diols, Such as ethanediol (ethylene glycol), ethylene glycol, diethylene glycol, neopentyl glycol, hi propanediol Propylene glycol), propane diol, 2,3-propane diol, 1,2-propylene diol, 1,3-propene diol, 2,3-propane diol, 1,4-butanone Alcohol, 1,3-butanediol, 1,2-butanediol, 2,4-butanediol, 10 200815497 25304pif Ο

/2 D: Alcohol, 3,4-butanediol, butylene glycol, 1,3-butenediol, di-alcohol, 2,4-butenediol, 2,3-butenediol , 3, 'butene diol, diol,! ·3 · Ethylene diol, amyl diol, 2, 3. Ethylene diol, alcohol, terpene diol, pentene diol, m pentene diol, ^ 戍 H 2, 4 _ Pentene diol, a substituted diol (such as 2-methyl, hydrazine diol) and a cyclic diol (such as 1,4-cyclohexane dimethyl hydrazine hexanol dimethanol, 1, 4) _cyclohexene diethanol), 1,6·hexane diol, diol (such as polyethylene glycol, polypropylene glycol, ethyl propylene glycol, polyethyl propylene glycol, ethylene propylene glycol copolymer and ethylene Butylene glycol = polymer), 1,4·cyclopentane dimethanol, cyclopentanyl dimethanol, u•cyclopropanediol, cyclopropanediol, cyclopropane dinonol, 1,2-ring Propane: 曱., 1,1-cyclobutanediol, 1,2-cyclobutanediol, cyclobutanediol, 1,2-cyclobutane dimethanol, 2_fluorenyl_ι, 2_ Butanediol, 3_mercapto-2,2-butane-alcohol, 1,1-cyclopentene diol, 1,2-cyclopentanediol, hydrazine, 3-cyclopentanediol, L2 - hexanediol, hydrazine, 3·hexane diol, U-cyclohexane diol, 1,2-cyclohexane-alcohol, 1,4-cyclohexane diol. The term "catalyst" is broadly understood to include any substance which increases the rate of reaction of an aliphatic carboxylic acid or the rate of polymerization of a polyhydroxy acid, but which is not consumed in the reaction. "Aggregation" and its grammatical variants are not only meant to mean "homopolymerization, but also to be copolymerized." This term is broadly understood to include the reaction of monomer molecules with each other or with a polymer chain of ceramide per acid. Any method by which a larger molecular weight polymer chain of a polybasic acid is formed. The polymerization mechanism may be cationic polymerization, anionic polymerization, coordination polymerization or radical polymerization. The polyhydroxy acid 200815497 polymer chain may be a linear chain or a three-dimensional network. Three-dimensional network polymer chain. For example, the above terms may include ring-opening reaction of a cyclic dimer with a polyhydroxy acid, thereby increasing the molecular weight of the polyhydroxy acid. The term "polymer" includes not only "all "polymer", also includes "copolymer,". The term "prepolymer" means a low molecular weight polymer comprising a monomer of a further polymerizable hydroxyclay monomer unit. Typically, the prepolymer has a molecular weight of less than about 100,000, more typically between about 15, and about 60,000. For example, the term "polylactic acid prepolymer, shall mean a polylactic acid having a molecular weight of less than 1 〇〇 5 , and which may be further polymerized to a higher molecular weight. The term "base group" describes when it is an organic compound. The functional group -OH in the case of a substituent, the term "coupling agent", refers to any agent capable of facilitating coupling between two or more prepolymers in a polymerization reaction. "5 isocyanate coupling agent" means that it contains atomic cerium

Exemplary diisomeric esters Any organic compound of isocyanate and polyisocyanate groups. U acidification of each private 6 f ‘ A _ U .

Cyanate S (hexamethylen

Benzene·W 12 200815497 25304pif

u diisocyanate, HMDI ) and tetramethylxylylene diisocyanate (TMXDI); alicyclic polyisoxic acid i such as isophorone diisocyanate (IPDI); aryl aliphatic polyisocyanate , such as xylene diisocyanate; and the above polyisocyanate modified by carbodiimide or isomeric cyanate; it may be used singly or in combination of two or more. Exemplary commercially available polyisocyanates are CORONATE HXTM and CORONATE HXRTM' both from Nippon Polyurethene Ind Co. Ltd. The term "polymerization conditions", and grammatical variations thereof, is defined herein to mean conditions such as temperature and pressure sufficient to promote polymerization of a polyamic acid. "Reaction zone" is broadly understood to include any region or space in which a dehydration condensation reaction of a polyhydroxy acid prepolymer occurs to form a high molecular weight polyhydroxy acid. Unless otherwise stated, the term "comprises" And its grammatical variants are not "open" or "included," so that they include the elements, and also include additional elements not mentioned. ~ As used herein, "about" in the context of a concentration of a formulation component generally means +/_5% of the indicated value, and more f is the indicated value, more typically +/_3% of the indicated value, more f is +/_2% of the indicated value, and even + is more indicative of the value of +M%, and is even more generally the 13th indication of the indication value, and should not be construed as a fixed limitation on the scope of the disclosed range. Therefore, it should be considered that the material of the village (4) is determined by the number of the villages and the individual values within the scope. For example, the description of the consumption of L, = to 6 has a sub-scope range, which is in the case of 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc. The individual figures in the range, for example, apply to any range of widths. Ο Ο 200815497 25304pif 2, 3, 4, 5 and 6. SUMMARY OF THE PREFERRED EMBODIMENT The method of MJI polybasic acid now discloses an illustrative, non-limiting embodiment for the manufacture of high molecular weight polyfilament acids, especially Doher II. Example: The polybasic acid in the molecule can be directly produced from an aliphatic group-based acid. In the example, this method can be used to directly manufacture arsenic 1 polylactic acid from lactic acid. The method comprises the steps of: condensing an acid-reducing agent with a functionalizing agent, and functionalizing it to be selected to form a pre-polymerized hydroxy acid having at least three terminal groups via a polyacid acid prepolymerized hydroxy acid. The polymerization is carried out in the presence of an ester coupling agent. Exemplary lipid ligament acids include, for example, lactic acid, glycolic acid, 2 ruthenium butyrate, 2 ruthenium reduction, 2 _ hexanoic acid, 2 dextroheptanoic acid, 2 _ carbazinamide: lacquer 2-曱Propionic acid, 2-hydroxymethylbutyric acid, 2·hydroxy-2-ethylidene-yi, 2-mercapto-2-methylpentanoic acid, 2 mercaptoethyl valeric acid, 2_radio-based 14 Ο u 200815497 25304pif-2-propylpentanoic acid, 2-hydroxy-2-butylpentanoic acid, 2-hydroxy-2-methylhexanoic acid, 2-based per-2-ethylhexanoic acid, 2-carboxy-2-propanyl Hexanoic acid, 2-hydroxy-2-butylhexanoic acid, 2-hydroxy-2-pentylhexanoic acid, 2-hydroxy-2-indoleyl heptanoic acid, hydrazine hydroxy group, ethyl 2-heptanoic acid, 2-hydroxyl group 2-propylheptanoic acid, 2-hydroxy-2-butenoheptanoic acid, 2-hydroxy-2-pentylheptanoic acid, 2-hydroxy-2-hexylheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 2-hydroxyl -2_ethyloctanoic acid, 2-hydroxy-2-propyloctanoic acid, 2-hydroxybutyloctanoic acid, 2-hydroxy-2-pentyloctanoic acid, 2-hydroxy-2-hexyloctanoic acid, hydroxy-2-heptyloctanoic acid , 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, >hydroxycaproic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methylbutyric acid, 3-hydroxyl -3-methylpentanoic acid, 3-hydroxy-3-mercaptoheptanoic acid, 3-hydroxyl group 3-ethyl valeric acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-3-ethylhexanoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-3-methylheptanoic acid , Ling Kesi ethyl heptanoic acid, trans- propyl heptanoic acid, 3-hydroxy-3-butylheptanoic acid, 3-hydroxy-3-methyloctanoic acid, 3-hydroxy-3-methyloctanoic acid, 3-hydroxyl group 3_propyloctanoic acid, 3-hydroxy-3-indolyl acid, = benzyl-3-pentyl octanoic acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 4-hydroxyhexanoic acid, hexaheptanoic acid, 4 -hydroxyoctanoic acid, pericyl group + methylvaleric acid, 'hydroxyl|methylhexanoic acid, 4_hydroxy-4-ethylhexanoic acid, 4 old base_4 methylheptanoic acid, cardio-yl-4-ethylheptanoic acid , 4_hydroxypropylheptanoic acid, 4-hydroxy-4-indolyloctanoic acid, 4-sided glacial ethyl octanoic acid, 4_recorded _4·propyl octanoic acid, • butyl butyl octanoic acid, 5- valeric acid , 5-carboxyhexanoic acid, 5 yl heptanoic acid, 5 octyl octyl hydrazide, 5' yl 5-methylhexanoic acid, 5 aryl j decyl heptanoic acid, 5 aryl group, ethyl group, 5-hydroxy group 5-mercaptooctanoic acid, 5-sided ketone ethyl octanoic acid, 5-hydroxyl group; propylene octanoic acid, 6-hydroxycaproic acid, 6-hydroxyheptanoic acid, 6-hydroxyoctanoic acid, 6-hydroxymethylheptanoic acid, 6- Methyl octanoic acid, 6-mercapto + ethyl octanoate , 15 15 Ο Ο 200815497 25304pif hexaheptanoic acid, 7-methyl octanoic acid, 7-mercapto _7-methyl octanoic acid, 8 _ octyl octanoic acid, other aliphatic silk fine, the mixture of (4) and the oligomerization of (10) Things. - These aliphatic silk filaments are optically active carbon in the molecular towel and are distinguished as the d_isomer axiSQmer), the L• isomer and the d/l-isomer form, respectively. Any of these isomers may be used in the disclosed method. The lipid acid may be lactic acid, which may be optically active D-lactide or toxic (ie, D acid vinegar). Or an optically active and inert mixture. The condensation step (a) may comprise the following steps: "The base acid is heated from the automaton to about 21 ° C, or from about 1 (10) C to about 200 ° C. The base == (8) can be carried out in an inert atmosphere, such as being injected through the condensation step (a) Packing the steps: empty. (10) When recording the acidity of the acid, applying a true vacuum to the acid reduction can be added at about 。1. In the embodiment, straight J; mHg to about 600 ugly range Apply. ~Work can be on about 5 sides Hg to about 200 mmHg

The passage of Phase)^*^^ (PaSsage), ^ground vacuum can also be used to increase the formation of water streams through the membrane. While promoting the permeate vapor stream (penneate vapor condensation step (a), the next step can be ascertained: 200815497 25304pif (a3) Stirring a mixture of a base acid and a functionalizing agent. The above is carried out at a rate of about 200 rpto. See condensation step (a The method may include the following steps: (a4) removing the condensed water formed during the polycondensation by vacuum and/or nitrogen. The condensation step (a) may include the following steps: Γ ( (8) when recording acid through the collateral cooperation, The silk catalyst catalyst can be applied to dehydration. The exemplary catalysts in the invention are metals, metal salts, hydroxides and cesium in Group 1, Group 11, m, ΙΜ and ν groups of the periodic table. And include, for example, zinc, tin, and other metals, such as tin oxide, antimony oxide, oxidized error = 'town, emulsified titanium and other metal oxides; chlorine "milk magnesium oxide, hydroxide, zinc hydroxide , oxime butterfly, hydrogen emulsified nickel, wind emulsified copper, oxidized hammer, ^ ̄: acid and other metal oxides; butterfly: sulfur: Qi and other metal samarium citrate f, carbolic acid ^ rhyme, milk _ and Other organic gen Fluorine / strontium sulphate To a poor person, monobutyltin oxide and upper 2 and other organic-acid metal salts, other organic metal oxides of the genus 4, the above-mentioned gold isothermal oxides and other metal alkoxides of the genus 200817497 25304pif , diethyl zinc and other metal alkyls of the above metals, and ion exchange resins. The amount of these catalysts in the liquid phase is in the range of 0.0001% by weight to 1% by weight. In an embodiment, the catalyst It is made up of tin octoate ( tin [II] 2-ethylhexanoate), tin chloride (2- tin [II] (tin [II] 2-chloride)), The group consisting of toluene-4-sulfonic acid monohydrate (TSA), octanoic acid, and zinc chloride is selected. The condensation step (a) may include the following steps: (a6) adding ε-hex Vinegar (ε-caprolactone). Advantageously, the addition of ε-caprolactone produces a mechanically tough and also ductile polymeric product. Importantly, the functionalizing agent should be carefully selected to ensure that the functionalizing agent and the hydroxy acid are present. At the time of the reaction, at least three of the four radicals are formed on the end of the prepolymer. To ensure that three hydroxyl groups are formed on the end of the formed prepolymer, the functionalizing agent should include one or more of the following: 〇 (i) polyol; / (ii) polyol and polycarboxylic acid (iii) Polyols and diols; and (iv) Polycarboxylic acids and diols. The composition of the functionalizing agent may be any of the following: (丨) one or more polyols; (u) 10 weights % to 90% by weight of the polyol and the balance being a polycarboxylic acid; (out) K) by weight to 9% by weight of the polyol and the balance being the diol; 18 200815497 253U4pli and (IV) 10% by weight to 90% by weight % polycarboxylic acid and the balance being a diol. - The prepolymer having at least three terminal hydroxyl groups is formed from an aliphatic hydroxy acid or an oligomer thereof. The prepolymer may be in a molten state (m加lten 5 ng, and may have a weight average molecular weight of 15, 〇〇〇 to 60,000. Advantageously, the prepolymer is formed from a hydroxy acid, and 25~〇. 0/〇 = prepolymer is a functionalizer containing at least three (four) energy end groups and / or, a 0.001 / 〇 diol monomer and / or 50 ~ 〇 · 〇〇! 0 / 〇 diacid Forming, wherein the molar number of the base is greater than the acid group. The method of the human body comprises adding an isocyanate oxime to the polyhydroxy acid formed to further polymerize the prepolymer by coupling. The polymerization step (b) can be The method comprises the following steps: (bl) heating the polyhydroxy acid from about ^ to ^25 〇. 〇, or heating from about 4 〇C to about 200 ° C, more preferably from about 16 『c heating to about 18 〇〇c. The polymerization step (b) may comprise the following steps:

Jb2) The polyhydroxy acid was stirred at a rotation speed of about 30 rpm. Step (b) may comprise the step of adding a pre-polymer or a polybasic acid ridge: a smectic agent (StablllZer). The stabilizer may be one or more peroxygen peroxides. The peroxides are taught by the published European Patent No. EP 0 737 and incorporated herein by reference. Advantageously, the addition of a peroxide slows down the amount of molybdenum, which will effectively stabilize the formed polyhydroxy acid by reducing the chain breakage (seissi°n). The peroxide as a stabilizer may have a short half-life gamma leg e). In the only example of 19 200815497 25304pif, the half-life of peroxide is less than i〇 seconds or less than $ seconds. Exemplary peroxides that can be used are organic peroxy compounds, and include, for example, lauric acid, tert-butylperoxy-diethylethylene H, second butylperoxy-2, Ethylhexanoic acid _, tert-butylperoxy isobutyrate, tert-butylperoxyacetate, tert-butylperoxybenzoic acid and diphenylguanidino peroxide. In a method, a method for producing polylactic acid from crude lactic acid (IV) is provided, which comprises the following steps: (a) agitation and at 50 ° C to 21 〇 t: or l 〇〇 t: to Heating at a temperature of 200 〇C to polymerize the crude lactic acid with a functionalizing agent to form a polylactic acid polymer having a molecular weight in the range of from 1 Torr to about 1 Torr; (^) to stir and at 1401 to 2501 or 140. (: to 2001: more preferably 160C to 180. (: at a temperature of between, polymerizing the polylactic acid prepolymer mixed with the vinegar coupling agent to obtain about 1 〇〇, 〇〇〇 to about 45 〇, 〇〇〇, or a polylactic acid having a molecular weight of from 150,000 to about 350,000. The inventors have observed that an increase in the prepolymer chain can reduce the amount of isocyanate coupling agent. However, a short prepolymer chain (i.e., less than / 1〇^(8) Molecular weight) The longer chain (that is, greater than 5 〇, 〇〇〇 molecular weight) is more mobile, so the reaction of the isocyanate hydroxy group is more likely to occur in the shorter prepolymer chain. In the case of theoretical limitations, the incorporation of at least three ^(tetra)f into the prepolymer allows the prepolymer, even the longer chain prepolymer, to be highly reactive. Therefore, it is more expensive than the short chain prepolymer. In the case of a hydroxy acid polymer, a polyhydroxy acid having at least three terminal hydroxyl groups 20 200815497 253U4pit is taken from a vehicle and a 1 (W e 1 ght) polyhydroxy acid polymer is more reactive in a shorter period of time. Alkaloid acid prepolymer can also be used for clothing & The coupling agent necessary for the acid polymer is reduced. * On the base of the acid; / An illustrative, non-limiting example of a reactor and system for carrying out the process for producing the above polyhydroxy acid will now be disclosed. The system comprises a reaction vessel having a reaction zone of a polymerization monomer mixture comprising a polymer having at least three terminal hydroxyl groups, a polymer and an isocyanide coupling agent. The reaction zone is formed by I The monomer mixture is operated under conditions of forming a high molecular weight polyhydroxy acid. The upper reactor may include a fluid jacket around the outer surface of the main 乂 4 knife of the enclosed chamber to receive the use therein. The liquid is heated. In use, the reaction zone is in a liquid in communication with the vacuum, and the reactor comprises a stirrer (agitat〇r) placed in the closed chamber to agitate the liquid phase used therein. Screw extruder. Cj different screw can be selected to obtain different required compression (c〇mpressi〇n). The extruder has an acid-resistant barrel and a screw, and the extruder screw The rods have a compression ratio of between about 1.5:1 and 3: 1. Likewise, different screw configurations provide different types of mixing. Some examples of screw designs include no mixing section, A screw having a mixing zone and two mixing zones. In one embodiment, the extruder is a twin screw extruder. Although a single screw extruder can still be used, it is relative to a single screw 21 For the 200815497 25304pif extruder, twin-screw mixing (4) offers the advantages of a more stable flow (4), easier feeding and better process control. This is due to the positive suction effect (p〇si^ve and lack of compression) resulting from the double enthalpy. An example of a non-linear twin-screw extruder is disclosed in International PCT Published Application No. WO/2003/035349. The non-limiting examples of the invention are further described in more detail with respect to particular examples and experimental examples, which are not to be construed as limiting the scope of the invention in any way. For example, although specific embodiments are described And experimental examples regarding the formation of polylactic acid, but it should be understood that the methods and apparatus disclosed herein can be used to make other polyhydroxycarboxyhe acids. Example 1 Feeding into a reactor having a capacity of 12 L under vacuum 9kg of 88% by weight commercial L-lactic acid (Archer Daniels Midland Co, Decatur, IL USA), 55 g 1,4-butanediol (99%, Lancaster) and 9 g glycerol (98/ί), Sigma-Aldrich And '9 g of stannous octoate (95%, Sigma-Aldrich) was added as a catalyst. The reaction mixture was heated at 100 C at a stirring speed of 200 rpm. The temperature was steadily increased from 100 ° C to 190 ° C under nitrogen bubbling. The vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg/h and then steadily increased from 1 〇〇 mmHg to 5 mmHg. The entire polymerization is about 20 hours to 40 hours. The condensed water formed during the polycondensation is removed by vacuum and nitrogen. A prepolymer having a Mw of 24,449 and a dispersibility of 1.37, 2008 2008 497 25304 ρί (polydisp-ersity) was obtained. DSC analysis indicated that the glass transition temperature of the prepolymer was 46.6 C' where the melting peak was at 141.4 〇C. Example 2, 3 kg of the prepolymer prepared from Example 1 was mixed with 86.1 g of hexakisium diisocyanate (99%, Merck). The mixture was fed into a twin-screw extruder (TE35, L/D=54, Coperion Keya (Nanjing) Machinery Co" ❹ LtcLN_ing, China), along the thirteen equally spaced temperature zones of the twin-screw extruder (equally spaced Temperature zones) have a temperature profile of 160-180-180-180-180-180-180-180-180-180-180-180-180-160 C and a rotational speed of 3Q rpm. The total time was about 8 minutes. The resulting product polymer was transparent 'having a Mw of 227 J89 and a polydispersity of 2.86. DSC analysis indicated that the glass transition temperature of the polymer was 5 〇t: Example 3 Polymerization was carried out as in Example 2 except that the amount of D of hexamethylene diisocyanate (99 〇/〇, Merck) was 84. 3 g. The resulting product polymer was transparent, having a Mw of 187,397 and 2.86. Polydispersity. DSC analysis indicated that the glass transition temperature of the polymer was 49 ° C. Example 4 - Feeding 9 kg of 88 kg of commercial L. lactic acid (ADM, USA), 50 g into a reactor with a capacity of 12 L 1,4-butanediol (99%, Lancaster) and 12 g glycerol (98%, Sigma_Aldrich) with 8 g as catalyst Stannous octoate (95%, Sigma_Aldrich). The reaction mixture was heated at 1 G (rc:T) at a stirring speed of 200 23 200815497 25304 pif rpm. The temperature was steadily increased from 1 〇0 to 19 在 under nitrogen bubbling. r. Increase the vacuum from 6〇〇mmHg to 1〇〇mmHg at a rate of 100 mmHg/h, and then increase from 丨00^111111^ to 5 mmHg. The whole polymerization is about 20 hours to 4 〇. : The condensed water formed during the polycondensation is removed by vacuum and/or nitrogen. A prepolymer having a Mw of 2 〇, 5 〇 8 and a polydispersity of 1.39 is obtained. DSC analysis indicates glass transfer of the prepolymer The temperature was 5 〇·5^, where the melting peak was at 141.7. (:. 〃 (Example 5) 80 g of the prepolymer prepared from Example 4 was fed into a Banbury mixer at a temperature of 160 C and a stirring speed of 20 rpm. Changzhou, China). When the melting is completed, L9 g hexamethylene diisocyanate (99%, Merck) is added to the uniformly mixed prepolymer, and then the temperature is raised to 180 ° C, and further Polymerization was carried out for 1 minute to obtain a product polymer having a Mw of 3, 3, 983 and a polydispersity of 5.01. DSC analysis indicated that the glass transition temperature of the polymer was 54.8 °C. U Example 6 3.54 kg of the prepolymer prepared from Example 4 was mixed with 99.1 g of hexamethylene diisocyanate (99%, Merck). The mixture was fed into the twin-screw extruder of Example 2, along the twelve equally spaced temperatures of the twin-screw extruder. The zone had 160-18 (Μ80·180-180-180-18 (M80-180-180_180) -18 (M80-160 ° C temperature profile and rotation speed of 30 rpm. The total reaction time in the twin-screw extruder is about 8 minutes. The resulting product polymer is transparent, it has Mw of 275,585 and 5·分散6 is more dispersible. ^sc 24 200815497 2^3U4plt analysis indicates that the glass transition temperature of the polymer is 52. 〇 ° C. &Example; Example 7 feeding 9 kg of 88 kg to a reactor with a capacity of 12 L 〇/0 commercial L-lactic acid (ADM, USA), 720 g of g-hexine (99% Lancaster), 62 g of 1,4-butanediol (99%, Lancaster) and 9.5 g of glycerol ( 98%, Sigma-Aldrich), and 9 g of stannous octoate (95%, Sigma-Aldrich) was added as a catalyst. The reaction mixture was heated at 100 ° C at a stirring speed of 200 rpm. The temperature was ramped from 100 C % to 190 C. The vacuum was increased from 6 〇〇 mmHg to 100 mm Hg at a rate of 1 〇〇 mmHg/h, and then steadily increased from loOmmHg to 5 mmHg. The entire polymerization was 2〇 hours to 4〇 hours by vacuum and / or nitrogen removal of the condensation water formed during the polycondensation. The obtained having 19,258

A polydisperse prepolymer of Mw and I·3. DSC analysis indicated that the prepolymer had a glass transition temperature of 35.9. (Example 8. 80 g of the pre-formed material prepared from Example 7 was fed into a Banbury mixer (Changzhou, China) at a /JHL degree of 16 ° C and a stirring speed of 20 rpm. When the melting was completed, 1 9 g of hexamethylene diisocyanate (99%, ^lerck) was added to the uniformly mixed prepolymer. The temperature was then raised back to 180 C ' and polymerization was carried out for 10 minutes. A Mw of 213,599 was obtained. And a polydisperse product polymer of 4. DS 7. DSC analysis indicated that the glass transition temperature of the polymer was 41 t. Example 9 In addition to the amount of hexamethylene diisocyanate (99%, Merck) used, 200815497 25304pif was 2 - 1 g, polymerization was carried out as in Example 7. The obtained product, the polymer was transparent, having a Mw of 254, 492 and a polydispersity of 4.49. DSC analysis indicated that the glass transition temperature of the polymer was 41 °C. Example 10 A 9 kg capacity reactor was fed with 9 kg of 88 wt% commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois USA), 60.5 g 1,4-butanediol (99%, Lancaster). And 5 g of quaternary, pentaerythritol (98%, Sigma-Aldrich) with 9 g added (Synthesis of stannous octoate (95%, Sigma Aldrich). The reaction mixture was heated at 100 ° C at a stirring speed of 200 rpm. The temperature was steadily increased from 1 ° C under nitrogen bubbling. To 190 ° C. The vacuum was increased from 6 〇〇 mmHg to 1 〇〇 mmHg at a rate of 100 mm Hg / h, and then steadily increased from 1 〇〇 mmHg to 5 mm Hg. The entire polymerization was about 20 to 40 hours. The vacuum and/or nitrogen were removed to remove the condensed water formed during the polycondensation. A prepolymer having a Mw of 21 916 and a dispersity of 1.4 was obtained. DSC analysis indicated that the glass transition temperature of the prepolymer was 51.6^, wherein The melting peak was at 141.33⁄4. 〇 Example 11 3.05 kg of the prepolymer prepared from Example 10 was mixed with & 5.7 g of hexamethylene diisocyanate (99%, Merck). The mixture was fed into the example? In the press, the thirteen equal intervals along the twin-screw extruder have a temperature of 160-180-180-18CM 80-180-180-180-180-180-. l8 (M8(M8〇-16〇) The temperature profile of ° C and the rotational speed is 30 rpm. The total reaction time in the twin-screw extruder is about 8 minutes. The resulting product polymerization 2 is transparent 'it has The scatter of Mw and 3.42 of 260,973. Dsc 26 200815497 25304pif Analysis indicates that the glass transition temperature of the polymer is 5L6t:. Example 12 400 g of 88 wt% commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illin〇is, USA), 0. 8 g of succinic acid (99%, Lancaster) were fed into a reactor having a capacity of 500 ml. ), 3.4 g of 1,4-butanediol (99%, Lancaster) and 0.2 g of pentaerythritol (98%, sigma-

Aldrich), and adding 0.4 g of stannous octoate as a catalyst (95 〇/0, Sigma-Aldrich). The reaction mixture was heated at 1 rpm under a stirring speed of 200 rpm. The temperature was steadily increased from loot: to 19 〇 C under nitrogen bubbling. The vacuum was increased from 600 mmHg to 1 〇〇 mmHg at a rate of 100 mmHg/h and then steadily increased from 1 〇〇 mmHg to 5 mmHg. The entire polymerization is about 20 hours to 40 hours. The condensed water formed during the polycondensation is removed by vacuum and/or nitrogen. A prepolymer having a Mw of 20,266 and a dispersity of 1.34 was obtained. The DSC analysis indicated that the pre-polymer had a glass transition temperature of 47 C' where the melting peak was at i47.4 °C. Example 13 80 g of the prepolymer prepared from Example 12 was fed into a Banbury mixer' (changzh〇u, (3) (10)) at a temperature of 16 Torr and a stirring speed of 20 rpm. When the melting is complete, h9 g hexamethylene diisocyanate (99%, = erck) is applied to the homogeneously mixed prepolymer. The temperature was then raised to 180 C and further polymerization was carried out for 1 minute. A product polymer having a dispersibility of 2 ιι, tearing Mw and 3·〇ι was obtained. The glass transition temperature of the dsc assay was 52.9 °C. Example 14 27 200815497 25304pif 400 g of 88% by weight commercial L_lactic acid (Archer Daniels Midland Co, Decatur, Illinois, USA), 2·7 g butanediol (99) were fed into a reactor having a capacity of 500 ml. %, Lancaster) and 0·25 g • glycerol diglycidyl ether (industrial grade, Sigma-Aldrich) with 0.4 g - stannous octoate (95%, Sigma-Aldrich) as catalyst. The reaction mixture was heated at 100 t at a stirring speed of 2 (8) rpm. The temperature was varied from 100 under nitrogen bubbling. (3 steadily increased to 190 ° C. The vacuum was increased from 600 mmHg to 100 mmHg at a rate of 100 mmHg / h, and then increased from 100 mmHg to 5 mmHg. The entire polymerization was about 20 hours to 40 hours. Vacuum and / or nitrogen ^ 'removed the condensed water formed during the polycondensation. A prepolymer having a Mw of 20,392 and a polydispersity of 1.42 was obtained. DSC analysis indicated that the glass transition temperature of the prepolymer was 49.5 ° C Where the melting peak is at 15 UX: Example 15 80 g of the prepolymer prepared from Example 14 ◎ was fed into a Banbury mixer (Changzhou, China) at a temperature of 160 ° C and a stirring speed of 20 rpm. 1. 9 g of hexakisyl diisocyanate (99%, Merck) was added to the uniformly mixed prepolymer. Then the temperature was raised to 180 ° C and further polymerization was carried out for 10 minutes. Mw having 215,962 was obtained. And a polydisperse product polymer of 2.79. DSC analysis indicated that the glass transition temperature of the polymer was 54.5 ° C. Example 16 Feeding 400 g of 88 wt% commercial L-lactic acid into a reactor having a capacity of 12 L (Archer Daniels Midland Co, Decatur, Illinois, 28 2008 15497 25304 pif USA) and 2.82 g of 1,4-butanediol (99%, Lancaster) with 〇·4 g as catalyst for stannous octoate (95%, Sigma-Aldrich) at a stirring speed of 200 rPm The reaction mixture was heated at 10 ° C. The temperature was gradually increased from loot: to 190 ° C under nitrogen bubbling. The vacuum was increased from 600 mmHg to 1 〇〇 mmHg at a rate of 1 〇〇 mmHg / h, And then steadily increased from 100 mmHg to 5 mmHg. The entire polymerization was about 20 hours to 40 hours. The condensed water formed during the polycondensation was removed by vacuum and/or nitrogen. Mw of 21.370 was obtained and 1.39 was obtained. Polydisperse prepolymer. DSC analysis indicated that the glass transition temperature of the prepolymer was 50.2 ° C, where the molten bees were at 15 ° C. 5 ° C. Example 17 Feeding 500 g into a reactor with a capacity of 500 ml 88% by weight of commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois, USA) and 6.65 g of pentaerythritol (98%, Sigma-Aldrich), and adding 〇·4 g as a catalyst of stannous octoate (95 g/g, sigma_Akirich) The reaction mixture was heated at i rpm (rc) at a stirring speed of 200 rpm. The temperature was allowed to rise from 1 Torr under nitrogen bubbling. (: Stabilized to 190 ° C. Increase the vacuum from 6 〇〇 mmHg to 1 〇〇 mmHg at a rate of 1 〇〇 mmHg / h, and then increase from 100 mmHg to 5 mmHg. The entire polymerization is about 20 hours Up to 40 hours. The condensed water formed during the polycondensation was removed by vacuum and/or nitrogen. A prepolymer having a polydispersity of Mw of 144 and ΐ3 was obtained. DSC analysis indicated the glass of the prepolymer. The transfer temperature was 49.5 ° C with a melting peak at 15 ° · 2 ° 。. Example 18 29 200815497 25304pif 76 g of prepolymer prepared from Example 16 and 4 g of self-example were prepared at a temperature of 160 ° C and a stirring speed of 20 rpm. 17 prepared active center oligomers fed into the Banbury mixer (Changzhou,

China). When the melting was completed, 2.1 g of hexakirylidene diisocyanate (99 /^>, Merck) was added to the mixture of the uniformly mixed prepolymer and the active center oligomer. The temperature was then raised to 18 deaths and further polymerization was carried out for 10 minutes. Get as many as 170,276] Viw and 3.73 Ο

Dispersible product polymer. DSC analysis indicated that the glass transition temperature of the polymer was 55 °C. Comparative Example 19 8 〇g of the prepolymer from Example 16 was fed into a Banbury mixer (Changzhou, China) at a temperature of 160 ° C and a stirring speed of 20 rpm. When the melting was completed, 2.1 g of hexamethylene diisocyanate (99% Merck) was added to the uniformly mixed prepolymer. The temperature was then raised to 180 ° C and polymerization was carried out for 20 minutes, wherein the sample product was collected at intervals of 1 minute. After 1 G minutes of polymerization, a product polymer having a Mw of 101,777 and a polydispersity of 2.17 was obtained. The DSC analysis indicated that the pre-polymer had a glass transition temperature of 54t. In addition, the product has a MW of 9,8 489 and a production of two fines of 2.43. The DSC / knife analysis indicates that the glass transition temperature of the polymer is 5 generations. It should be understood that because this comparative example is only 佶 ^ ^ y ^ , ^L^ 平乂 I Wang, for example, only use diol to form prepolymerized-uu A 低 into a low molecular weight polymer. Therefore, the pre-four, δ objects do not have three terminal groups. And therefore it is not possible to obtain high molecular weight polylactic acid in this comparative example. 30 200815497 25304pif Example 20 Feeding 9 kg of 88 wt% commercial L-lactic acid into a reactor with a capacity of 12 L (Archer Daniels Midland Co, Decatur , Illin〇is, USA), 19.5 g 1,4-butanediol (99 〇/〇, Lancaster) and 9 〇g pentaerythritol (98%, Sigma-Aldrich) with 8 g of stannous octoate as catalyst (95%, Sigma-Aldrich). The reaction mixture was heated at 100 ° C at a stirring speed of 200 rpm. The temperature was ramped from 1 ° C to 190 ° C under nitrogen bubbling. The vacuum was made 100 mmHg. /h rate increased from 600 mmHg to 1〇〇mmHg, and then increased from 1〇〇mmHg to 5 mmH g. The entire polymerization is about 20 hours to 40 hours. The condensed water formed during the polycondensation is removed by vacuum and/or atmosphere. A prepolymer having a Mw of 43,923 and a polydispersity of 1.72 is obtained. Analysis indicated that the prepolymer had a glass transition temperature of 53.lt with a melting peak at 148 ° C. Example 21 1.9 kg of prepolymer prepared from Example 20 with 36.5 g of hexamethylene diisocyanate (99%, Merck) Mixing. The mixture was fed into a twin-screw extruder (L/D=40, Jieya, China) with six equal-temperature zones along the twin-screw extruder with l60_175_18〇_18〇_18〇_175_165t: The temperature profile and the rotational speed were 60 rpm. The total reaction time in the twin-screw extruder was about 2 minutes. The resulting product polymer was transparent with a Mw of 284,767 and a dispersibility of 5.37. DSC analysis The glass transition temperature of the indicated polymer was 56 T: Example 22 A reactor with a capacity of 12 L was fed with 8876 g of 88 weight 0/〇31 ο ο 200815497 25304pif commercial L-lactic acid (Archer Daniels Midland Co, Decatur, Illinois , USA ), 19.5 g D::: complete diol (99%, Lancas Ter ), 250 g g _ caprolactone (99%, Lancaster) and 9·0 g pentaerythritol (98〇/〇,

Sigma-Aldrich), and adding 8 g of stannous octoate as a catalyst (95%,

Sigma-Aldrich). Heating at 10 (rc) at a stirring speed of 200 rpm

Reaction mixture. The temperature was steadily increased from 1 ° to DO °C under nitrogen bubbling. The vacuum was increased from 600 mmHg to 100 mmHg' at a rate of 100 mmHg/h and then steadily increased from l〇〇mmHg to 5 mmHg. The entire polymerization is about 20 hours to 40 hours. The cold/spin water formed during the polycondensation period is removed by vacuum and/or nitrogen. The crucible has only a prepolymer having a Mw of 47,242 and a dispersibility of 1.75. DSC analysis indicated that the prepolymer had a glass transition temperature of 48.1 °C. Example 23, 8 〇g from Example 22 at a temperature of 16 (TC and agitation speed of 2 rpm)

Banbury (Changzhou, China) Z II's singularity, the L0 g hexamethylene diisocyanate (99%, :iJ" added to the average-mixed prepolymer. The product was further polymerized for 5 minutes to obtain a product polymer having a polydispersity of 252,322. (4) Analysis indicates that the polymer has a break transfer temperature of 50.5 t: Application (Applicati_) The manufactured product has a polymer TM It can be used in machinery such as medical equipment, 200815497 25304pif Moreover, the disclosed method is effective for preparing high molecular weight polybasic acid, prepolymer and lactic acid which have little loss from the system in the pot. Soil - The disclosed method can form high molecular weight: The expensive r step (that is, the method disclosed by the lactic acid vinegar forming high text m does not use multi-unit operation (4) umt 〇peratlons) (ie distillation tower, evaporation cry, 埶6 (^P|LS^S|) Ο

CJ method than other molecular weights _ lactic acid square green = the short polymerization time of the prepolymer converted to polylactic acid, U. / / No later miscellaneous equipment to handle high viscosity polylactic acid products. High molecular weight poly-wei is produced due to over-unit operation. The reactor It takes place in a reactor followed by a twin screw extruder. The right 2 _ system and method are relatively easy to operate and maintain. By-products, the disclosed systems and methods do not produce any environmentally harmful stomachs. 'After the disclosure of the technical field of the present invention, it should be apparent that the present invention will not be changed to any other changes and modifications of C. All i 卞 知 知 知 知 知 知 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 33 33 33 33 33 33 33 33

Claims (1)

200815497 25304pif X. Patent Application Range: ι· A method for producing a high molecular weight polyhydroxy acid, comprising the steps of: (a) condensing a hydroxy acid with a functionalizing agent, the functionalizing agent being selected = forming a polyhydroxy group after the condensation An acid prepolymer having at least three terminal hydroxyl groups on the polyhydroxy acid prepolymerized octazone; and (b) forming the prepolymer in the presence of a coupling agent under formation of the high molecular weight polyhydroxy acid Perform polymerization. A method of producing a high molecular weight polyhydroxy acid as described in claim 1, wherein the coupling agent is an isocyanate coupling agent. The method of manufacturing a high molecular weight poly-based method according to the invention, wherein the functionalizing agent comprises a polyol, and optionally at least one or both of the acid and the second fermentation. The combination of alcohol is more than tick. ^4" The method for producing a high molecular weight polybasic acid according to the first aspect of the patent application, wherein the formation >#1, the weight of the spoon i = the amount of 6 molecular weight polyfilament acid has a range of at least o In the sub-amount of the high molecular weight polybasic acid described in Item 1, the poly-light acid has a _ 〇 彻 , , , 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬 酬The alcohol is selected from the group consisting of - _ ^ alcohols, aromatic diols and mixtures thereof:: hexa-alkane ii. 7. The method of manufacture, wherein the glycerol is a molecular weight multi-basic acid Alcohol, branched or linear propanediol 铯 free oxime substituted ethane dibutane diol, pentane diol, hexane dioxime 200815497 25304pif alcohol, octyl alcohol and mixtures thereof Ethnic group. • The high-scoring manufacturing method described in claim 6 of the patent scope, 苴中兮; 丁 夕 羟基 hydroxy acid, cyclo diol is selected from cyclopropyl hydrazine, which is optionally substituted Alcohol, cyclopentanediol, cyclodecanediol, cyclooctanediol and metadiol, cycloheptane 9. As claimed in the patent scope; The method of producing, wherein the aromatic diol is a group consisting of benzene and a second wire bismuth selected from the group consisting of dibasic polyhydroxy acids. - "Fabric benzene, diuretic linkages. 10. For the manufacturing method of the patent application (4) 3, wherein the polyol is a sub-quantity polyglyceride, triglycerin m pentaglycerol and hexaerythritol, glycerol, dioleate And the group formed by its mixture. The method of manufacturing the octagonal glycerol hexahydrate according to the ninth aspect of the invention, wherein the condensation step (a) the amount of the polyhydroxy acid of the knife (al) is from the hydrazine. . Add:::Steps: 12·If you apply for the ancient 2 as described in Item 11 of the patent scope. a manufacturing method in which the heating step (a singular amount of polyhydroxy acid 13 is carried out in a green atmosphere as in the application of the first item of the patent range), wherein the condensation step / the molecular weight of the ruthenium The hydroxy acid (10) when the can is functionalized with the functionalization: a vacuum is applied. The reaction is known to the hydroxy acid. The manufacturing method of the hydroxy acid is as described in claim 13 wherein the vacuum is at the 〇a The molecular weight polyhydroxy acid is in the range of 600 mmHg (80 kPa). mIig (〇·〇13 kPa) to 200815497 25304pif 15. The method for producing a high molecular weight polyhydroxy acid according to claim 1, wherein the condensation step (a) comprising the steps of: (a3) stirring a mixture of the hydroxy acid and the functionalizing agent. ^ 16. The method for producing a high molecular weight polybasic acid according to claim 1, wherein the condensation step (a) comprising the steps of: (a4) providing a catalyst to the hydroxy acid when the hydroxy acid is polymerized. The method for producing a high molecular weight polyhydroxy acid according to claim 16, wherein the catalyst is suitable 18. The method for producing a high molecular weight polyhydroxy acid according to claim 16, wherein the catalyst is stannous chloride, stannous oxide, tin powder, cerium oxide, iron oxide, zinc acetate. Or a method for producing a high molecular weight polyhydroxy acid as described in claim 1, wherein the condensation step (a) comprises the step of: (a5) adding ε-caprolactone. The method for producing a high molecular weight polyhydroxy acid according to claim 1, wherein the functionalizing agent comprises one or more of the following: U (i) a polyhydric alcohol; (ii) a polyhydric alcohol and a polycarboxylic acid; (iii) a polyol and a diol; and (iv) a polycarboxylic acid and a diol. The method for producing a high molecular weight polyhydroxy acid as described in claim 1, wherein the condensation step (a) is carried out. The method for producing a high molecular weight polyhydroxy acid as described in claim 1, wherein the prepolymer has an average molecular weight of from 1 〇, 〇〇〇 to 100,000 and 36 200815497 25304 pif. 23. If you apply for a patent The method for producing a high molecular weight polyhydroxy acid according to Item 1, wherein the polymerization step (b) comprises the following steps: (b) heating the polyhydroxy acid from 140t: to 250 ° C. The method for producing a high molecular weight polyhydroxy acid according to claim 2, wherein a molar ratio of the isocyanate group in the isocyanate coupling agent to the hydroxyl group in the prepolymer is from 0.5 to 1.5 or from 0.8 to 1.2. The method for producing a high molecular weight polyhydric acid hydrazone as described in claim 1, wherein the polymerizing step (b) comprises the step of: (b2) into the prepolymer or the polyhydroxy acid formed Add stabilizer. 26. A process for the manufacture of a high molecular weight polyhydroxy acid as described in claim 25, wherein the stabilizer comprises one or more peroxides. 27. The process for producing a high molecular weight polyhydroxy acid as described in claim 1, wherein the polymerization step (b) is carried out for 1 minute to 30 minutes. 28. A system for making a high molecular weight polyhydroxy acid, comprising: a reactor having a reaction zone of a polymerized monomer mixture comprising a polyhydroxy acid prepolymer having at least three terminal hydroxyl groups and A coupling agent, wherein the reaction zone is operated under conditions in which the high molecular weight polyhydroxy acid is formed from the polymerizable monomer mixture. 29. The system for making a high molecular weight _ polyhydroxy acid according to claim 28, wherein the coupling agent is an isocyanate coupling agent. 30. A system for making a high molecular weight polybasic acid according to claim 28, wherein the reaction zone is in a liquid in communication with the vacuum. 37 200815497 25304pif 31. A high molecular weight polyhydroxy acid produced by a process comprising the steps of: (a) condensing a carboxylic acid with a functionalizing agent, the functionalizing agent being selected to have at least a polyhydroxy acid prepolymer having three terminal hydroxyl groups; and (b) polymerizing the pigment in the presence of a coupling agent under conditions to form the high molecular weight polyhydroxy acid. 32. The high molecular weight polyhydroxy acid of claim 31, wherein the coupling agent is an isocyanate coupling agent. 38 200815497 25304pif VII. Designated representative map: (1) The representative representative figure of this case is: no designated representative figure (2) The symbol of the representative figure is simple: no eight. If there is a chemical formula in this case, please reveal the best indication of the invention. Chemical formula: