US0057710682A United States Patent 119; fi) Patent Number: 5,770,682 Ohara et al. 145) Date of Patent: Jun. 23, 1998, [s!] METHOD FOR PRODUCING POLYLACTIC. [56] References Cited ACID [75] Inventors: Hitomi Ohar ‘yoto; Se eee Obtst; Masahiro Ho; Yasuhiro Fy 5.386004 11905 Otc sovnss both of Kyoto; Masaaki Oota, Mukous Hideshi Yamaguchi, Chobu, all of Japan [73] Assignee: Shimadzu Corporation, Kyoto, Japan [21] Appl. No. 678,328, [22], Filed: Jul 11, 1996 [30] Foreign Application Priority Data PL pan (P| apa taP| ape pa12is LP] dopa 731182 ‘Co8G 63/08 “S2N/3S4, 528035 528/354, 357, 528/361 [58] Fleld of Searen Primary Examiner—Due Tevong, Attorney, Agent, or Firm Bec, Stewart, Kolasch & Birch, uP [57] ABSTRACT. ‘A method for producing « polylactic acid, comprising the steps of carrying out ring-opening. polymerization of Tactde to give polylactic acid, adding 4 compound capable of inactivating & catalyst for ring-opening polymerization of laatide atthe completion of the reaction, and removing unchanged lactide from the polylactic acid product by pressure andr allowing an inet gas to pass; and 34 for forming fiber or film diretly fom the poly- Tactic acid produced by the invention. 18 Claims, 1 Drawing Sheet Vac 15 mmHg 80-110°C Vac 15 mmHg 4 Lactide 21 80110'C 76 Catalyst 1 160°C =| 8 Net Okgf/em* i Vv 25 13 9 12 8 — 10 18 24 -@ 1 16 17 23 20 207 20U.S. Patent Jun, 23, 1998 5,770,682 Vac 15 mmHg 80-110°C Vac 15 mmHg Cy Loctide 21 80110 76 ZA Catalyst { # 1 160°C =| A ee N,10kgf Jom 25 iT 24 17 22 33 = 20 2 FIG.15,770,682 METHOD FOR PRODUCING POLYLACTIC ACID BACKGROUND OF THE INVENTION 1, Field of the Invention The presen invention relates to a method for peeducing 2 sol, thermostable polylactic acid having a high molecular ‘weight. The polylactic acid obtained by the present method ‘can take Various shapes such as granular, pelletized, and plate-like forms, and is useful as a bio-compaible and biodegradable polymer. The presen invention also relates toa method for diretly spinning sad polylatic aid into threads or drectly forming, fms therteom, 2, Discussiow ofthe Related Art Polylactc acid isa biologically very safe polymer, and its egradated product, namely let acd, is absorbed in vivo. Having above propertics, the polylactic acid is useful for medical purposes, including surgical sutuces, sustained release capsules in drug delivery systems, and reinforcing materials for bone fractures. Moreover, it is noted as & degradable plastic, because it is degraded vader natural ‘environmental conditions. Its also widely used for mono= axially and biaxially stretched films, fibers, extrusion products, and various other purposes. In the production of the above various formed products, mechanical properties ‘equivalent to those of widely used resins are required forthe polylictic seid. In order to achieve the desired mechanical properties, high-molecular weight polylactic acid with litle thermal decomposition upon forming are in demand, Methods for producing polylactic acid are known as follows: In one method, lactic acid is directly subject to ehydation condensation to give a desired product. In anolter method, a cyclic lacie is first synthesized from lactic acids and then purified by such metbods as ysiallization, followed by ring-opening, polymerization Various procedures for sythesizing. purifying and polymer- izing lactdes are disclosed in US. Pat. No. 4,057,537, EP-A.261,572, Polymer Bulletin, 14, 491-495 (1985), Mak ‘romol. Chem., 187, 1611-1628 (1986), ad other chemistry Titeratces. Also, JP-B-S6-14688 discloses a method for producing polylacic acid comprising polymerizing a bimolecular cyelic diester, as an intermediate, using. tin ‘ctylate of lauryl alcohol asa catalyst. Also, polyactc acid ‘ean be produced directly From lactic acid by the methods 25 described in JP-7-33861, 3P-59-96123, and The Proceedings of The Discussion on Macromolecules, vol.44, pp3198-3199. ‘The polylaete acid thus obtained i pelletized into various forms, such as spheres, cubes, columns, and disrupted pisces, in a size from a rice grain to a bean, to make its handling easy inthe forming process. ‘When the polymerization of lati seid is catied out a1 hig temperature, e., 180°C, acide is produced owing to depolymerization. Also, polylactic acid having a high molecular weight of 100,000 io $06,000 fas a high melting poiat of 175° to 200° C. Conventionally, when the tna) polymer product of the above polylacie acid is taken out of the reactor in a molten state and heated to a temperature higher than its melting point, dhe polylactic acid undergoes ‘decomposition and coloration, Moreover, a lange amount of Inctide is generated from the polymer at the above high temperatures presumably owing tothe fact that polymer. Tactide equilitium is shifted toward the Isctde side atthe above temperatures, 2 ‘Those letde and decompsition products thereof are lable o sublime daring injection mong or epinng ofthe pololacti aid pellets used a «stating material and unde Siably adhere to dice or nozzle, and thereby the operation ishampered Furthermore the lacie and te decomposition products ower the alas asco temperature ad te melt ‘iscsi ofthe polymer, esulig in drastic deterioration of Imoldability and thermal sabiity. Also, gasified low Inolecular components, sich as atid, adversely ffest he ‘woreplace environmen ‘When polymerization proeuds wo a desired molecular ‘weight ian vertical reactor, the viscosity of the pret «exceeds 30,000 pose at tection temperature of fo 120° to 160" C., necessitating sitong stirng. Thus, te highly ‘isons poiymer prodict dees tothe internal srface of the reactor and ming impellers tbereby causing decrease in yield, and the necessity of exira steps sich 8a cleaning step, and coloration of the product. Tn an attempt to save the above problems, JP-A-3-14829 discloses « method where the polymerization produet of lyeolde or let, which isin s molten sae, Weated Inder reduced presi. In another attempt polyelyeoide ismelied under fedyeed presi to remove fow-moleculr components by distillation Kagabu Kogatu Zasshi 72), 362 360(1964)] ‘The methods above, however, canoo! sulicienly remove low-matecular components sich as letide without inet vatiag the catalyst used forthe polymerization, because laside i in equilibrium with polylacte aid ad the equi lium is catalyzed by the catalyst ‘As 4 method for conkolling, the eatlyst activity for polymerization, IP-B-8-13963 discloses that» phosphoric {id or phosphorous acid compound is added to the reaction mixture atthe time when the molecular sight of the polymer reaches 2000 Yo 6000 an tbat the polymerization proceeds. However, this prior art metboa Aiected to the predction of polylacic acd by diet polymerization of late ei, which is quite dierent fom the method ofthe preset invention creed to the produc tion of plglate seid by dag-opening polymerization of tact. Also, the purpose of th prior a meth i low the rte ofthe polymerization reaction by ang the phos- pore cid or phosphorous ack compound at the ide When the molecular weight ofthe polymer is stl low. Ts, tis prior art method isnot directed to efiien removal of the lowemclecular components, such a ate, rom the poly rer ading phosphoric acd el. to inactivate the caalyst completely and hence to stop depolymerization reaction ‘ompleely. SUMMARY OF THE INVENTION ‘An object of the present invention is to provide method for producing a polylactic acid having a high molecular ‘weight and high theemal stability, which is feee from coloration, contains substantially no decomposition prod- ucts or lacie, anal has a desired shape appropriate toa final product. ‘As 4 result of intensive research in view of the above ‘object, the present inventors have found that polylctc acid Tree from coloration and containing substantially no decom position products can be oblained by removing. low- Iolectlar components, manly lactde, by reducing presse andlor allowing an inert gas to pass through the reaction mixture during or after polymerization process. Also, the present inventors found that depolymerization ofthe product ‘can be suppressed by adding a compound expable of low-5,770,682 3 ring the catalyst activity when a weight-average molecular ‘weight of the polylacti acid produced i 50,008 or more ‘The inventors also found that the compounds capable of suppressing depolymerization of polylactc acid incu (a) phosphoric ack or phosphorous acic, or the derivatives ‘thereof; and (b) aluminum compounds. Based upon these findings, the present invention has been completed In one embodiment, the present invention relates to a method foe producing polylactic acid, comprising the steps ‘of earrying out ring-opening polymerization of lctde to tsve polylactic acid, adding 4 compound capable of inaeti= ‘ating. # catalyst for ring-opening polymerization of the Tact, and removing unchanged Late from the polylactic acid prodct by reducing pressure andor allowing an ince, {B88 (6 passthrough the reaction mixture. In another embodiment, the present invention relates to a method for forming fer or film directly from the polactic ‘acid priced by the method above ‘According 10 the method of the present invention, & formed, particularly pelletized, polylatic acd having a high ‘molecular weight of 200,000 to 500,000 free from coloration ‘and conning subsiatially no decomposition peoduels can be oblained BRIEF DESCRIPTION OF THE DRAWINGS FIG. Lisa sehen for tic view of an example ofthe apparatus ying ont the method ofthe present invention DETAILED DESCRIPTION OF THE INVENTION Inthe present application, the tem “unchanged lnctide™ refers to not only letde a8 4 starting material monomer but abo lactde as 4 decomposed product of polylactie acid. ‘The polymerization temperature in the production method ‘of polylati acids in accordance withthe presen invention isin the range of 120° to 180" C, Polymerization is preter- ably carted out inthe range of from 140" 10 160% C. 10 prevent racemization, decomposition and coloration of [sctide,Polylaetic acd having a weight-average moteea- lar weight of 50,000 10 300,000 are obtained by polymer- ination. Polymerization is performed by using one or more Vertical reavtors and terminated before the polylactic acid Fhecomes too viscous o How easily. I is preferable to use 4 plucality of reactors with impellers adapted to different viscosities, since the viscosity of polymer increases a8 polymerization progresses. Furthermore in the case of con Tinuows operation, « plurality of reactors are connected in seties soa o make the distribution of retention time sharp and extend the area for heat irsfer per volume, For ‘example, reactor wit a slanted impeller, turbine impeller ‘ora full zone impeller i used isto uniformly sie aeatalyst ‘when the viscosiy is low. Next a reactor with an impeller ‘dapted wo high viscosity, such asa spiral eibbon impeller, is used for siering, When a plurality of reactors are used itis not always necessary to make the reaction temperatures of the reactors equal. With espect to catalysts used in the polymerization ofthe preseat invention, a catalyst comprising at least one metal ‘cleced from the group consisting of an clement of group IA, ‘ofthe periodic table, an element af group IVAof the periodic table, an elemet of group IVB of the periodic table, and an cleat of group VB of the periodic abl; or 3 compound thereof is used Examples of the catalysts comprising a metal of group IVA or 4 compound thereof inclide organotin compounds, 4 cate, in tartrate, tn dicapryat, tin dilaurate, i distearte, tin dioleat, tin a-naphthoate, tin f-naphitoste, and tin octyate; and tn powder Examples ofthe catalysts comprising a metal of group LA ‘or « compound thereof include hycroxides of alkali metals, such as sodium hydroxide, potassium hydroxide, and Tithium hydroxide, weak acid sills of alkali metals sich a8 sodium lactate, sodium acetate, sodium carbonate, sodium ‘ctylate, sodium stearate, polassium Iatate, potassium potassium carbonate, am potassium oktylate, and alkoxiies of alkali metas, such as sodium methoxide, potassium methoxide, sodium cthoxie, and_ potassium thoi Examples of the catalysts comprising a metal of group IVB include titanium compouncs, such as teirapropyl titanate, and zirconium compounds, Suc 3s zirconium iso- propoxie Examples ofthe catalyst comprising « metal of group VA include antimony compounds, sich 38 antimony lrioxke All the above catalysts are conventionally used in poly- ‘merization of lactic acids. Among them, catalysts compris- ing tino & compound thereot is preferably used in ems of catalyst activity: Also, the molecular weight of the final polymer product can be changed by the amount of catalyst added, Smaller the amount of catalyst used is, higher the ‘molecular weight of the polymer product is, though the reaction rate decreases, Nueleating agents, seh tale, lay, and titanium oxide, may be optionally added. "The lactic sed for the method of the present invention may be a Dey L-, or DLvisomer, or a mixture of D- and Lisomers. The above monomer ean also be copolymerized with lactones, such 28 B-propiolacione, 6-valerolaetor ‘e-caprolactone glyeolide, and &-bulyrolacton, dicarboxylic acids, diols, hydroxy carboxylic acs, and aliphatic poly- esters. Further, polynydrc aleobols, such as glycerol, may be used to contol physical properties The conditions for polymerization depend on the catalyst used. When tn oetylate is used a the catalyst, polymeriza~ tion is catia oat by beating the reaction mixture normally {or 1.0 to 30 bours using the catalyst in an amount of from (0.0001 to 5% by weight preferably [rom 0,005 t0 0.15% by ‘weight, based on the lactide. ‘The reaction is preferably carried out in an atmosphere or stream of an inert gs, seh as a nilrogen pas. ‘When the polymerization reaction is terminated (Gor ‘example, when the molecular weight has reached 50,000 or mor, preferably when the amouat of unchanged late has reached 10 10 50 wt %), the unchanged lactide is removed by pressure eduction using a Lavweiype thin-film evspo- ‘ator ora horizontal single- or dualeaxs reactor adapted to highly viscous Mus under reduced pressure of 1 10 200 smmilg. The melting point of the product rises as he lctide FR removed. When the product is retained at a temperature higher than its meling point for an extended peri of time, depolymerization occurs aad lictde is generated again, Therefore, when a plurality of horizontal reactors are con= nected in series, itis preferable that the reactant in each reactor should be subjected to reaction atthe lowest tem perature that allows te reactant tobe i the molten state. In aditio, when single extruder is used to remove monomer, itis preferable that the temperatures of the barges thereol be ‘sed stepwise in the direction from the inlet for the reactant to the outlet for the produet. In tis case, the temperatures are inthe range of 140° to 220° C. When two horizontal reactors ace used ina two-stage configuration, the fist stage cen be provided with 4 reactor with a spectacle impeller or5,770,682 5 44 reactor with a grid impeller made by Hitachi Lid, or an IN-SCR or HVR made by Mitsubishi Heavy Industries, Ld, ‘ora Bivolac made by Sumitomo Heavy Lodustries, Ltd. A ‘conventional exiader can be used for the second sage. Mainly, unchanged lactde is removed and captured by @ ‘cooling condenser eyelone or the like, al then subjected 10 tmelt polymerization again, ‘The polylactic acid is in equilibrium with letde in & molten state. When estalytic tivity is high, lactde is re-generated, even after itis removed. To remove laetide clients, itis therefore necessary to remove lactide at @ higher rate than itis e-generated, To facilitate this, the catalytic activity i suppressed by adding the following ‘compounds when the weight-average molecular weight of the produet polymer reaches 50,008 or higher: (8) phospho- re acd or phosphorous acid, or the derivatives thereof; and (©) aluminum compounds. These compounds are added in an amount of O55 to 20 times by weight of the amouat of the catalyst used. Specifically, in case where the compound ted isa phosphoric acid compound and he catalyst tn ‘compoud, the molae ratio of tia compound to phosphoric ‘acid compound isnot higher than 0.9, preferably inthe range ‘of from 0.05 to 08. Examples of (a) phosphoric acid or phosphorous acid, oF the derivatives thereof inclule phosphoric acid, phospho rous acid, pyophosphorc aid, polyphosphorie acid, mono ethyl polyphosphate, diethyl polyphosphate, tciethy] Phosphate, tripbeayl phosphate, ftracthy! pyrophosphate, letraphenyl pyrophosphate, tsimetbyl phosphate, methyl phosphite, ethyl phosphite, triphenyl phosphite, hexam cllamide pyrophosphate, adenosine triphosphate (ATP), ‘eiealeium phosphate, esleium phosphinate, disodium phosphate, monostearic acid phosphate, distearic acid (Phosphate, treo-butyl phosphate triphenyl phosphite, triph ‘ny phosphate, diethyl phosphite, dibuyl phosphite tci- ethyl phosphite, tributyl phosphite, dipotassium hydrogenphosphate, potassium dihydrogenphosphate, poasium pyrophosphate, calcium phosphinate, calcium pyropbosphate, disodium hydrogenphosphate, sodium ihydogenphesphate, aluminum phosphate, slumiaum dihydrogenphosphate, and bis(3,5-dict-butyl-a- hydroxybenzylphosphoric acid eth!) ealeium. Examples of () aluminum compounds include aluminum phosphate, aluminum dihydrogenphosphate, aluminum ‘oxide, aluminum lactate, suminum aectylacetonate, slum num fore, aluminuan iodide, aluminum sterat, alumi: num it-butoxide, aluminum tr-s-butoxide, aluminum Iwiethoxide, and aluminum tisopeepoxie, esis the compounds of (2) ard (b) above, oxidizing agents such as dibenzoyl peroxide may be used ‘The above compounds may be used singly or in combi nation of to oF more kinds The polylactic acid obtained by the method explained shove may be formed into film or fiber through a dic. For ‘example, fibers are spun a a spining rate of from $00 to 41200 m/min, and drawn ata draw ratio of from 3.0 to 45, Als, the obtained polylatic seid may be formed into & desired shapo, such as granular and pelletized forms, using ‘forming machine In adit, conventionally known adkltives, including sabilizers, such as calcium stearate; plasticizers, such as philic acid ester; and coloring agents, such as chromiam ‘orange and titanium oxide may be akled © the polylactic ‘id FIG. 1 is a schematic view showing an apparatus for carrying out the method of the present invention. Referring 6 0 FIG. 1,» preferred embodiment of the present invention is herwinaiet desribed in detail In the figure, A and B designate vertical reaciors mainly used for polymerization, and C and D designate horizontal reactors mainly used for removing unchanged lactide under reduced presse "The reacior A comprises a hollow eylindical reaction ‘aok 1, and the reaction tank 1 is provided with a material supply inlet 2 and a discharge opsning 3. To the discharge ‘pening 3, a discharge nozzle § Is connected. The novzle § is provided with a valve V for controlling polymer to be supplied to the next reactor B. To the material supply inlet 2,'t material supply pipe 14 is connected. The pipe 14 is provided with openings 6, 7 connected to recovery pipes for recovering wochaaged lati, and is also provided with an ‘opening 21 connected to estalyst supply pipe "Afull ze impeller 4is housed in the reaction tank 1. "The dive source (motor) M thereof is insalled on the side of the ther opening. Arouod the circumference of the reaction tank eater (heat medium jacket ot shown) is provided to beat the reaction tank 1. In addition, the temperate inside the reaction lank 1 i monitored by a lemperature sensor (aot shown). Like the reactor A, the reactor B comprises 2 hollow cylindrical rection tank 8. The reactor Bis provided with supply inlet 9 for supplying polymer from the reaction tank 1 and is aso provided witha discharge opening 10. To the lscharge opening 10, s connection pipe IT connected 10 the ‘ext reactor C i connected, The conaeetion pipe UL is provided with a gear pump P.Aspral ribbon impeller 12 is housed inthe reaction tank 8. The dive source (motor) M therea i installed on the side of the other opening of the reaction tank 1. Furthermore, to the reaction tank 8, 3 nitrogen gas suppl pipe 13 is connected s that nitrogen gas is supplied from a gas eylinde (oot showa) to the tank 8 via the pipe. Like the reaction tank 1, the reaction tank 8 is provided with a heater (not shown) dad a temperature sensor (oot shown). The horizontal reactor Cis provided witha supply inlet 16 for sipplying polymer from the reaction tank 8 andi also provided with a discharge opening 17. To the discharge ‘pening 17, a connection pipe 20 connected to the next reactor D is connected, Furthermore, the horizontal reactor Cis provided with an opening 18 used to reduce pressure in the tink aod connected ta 4 recovery pipe 19 for returning removed unchanged lictde to the reaction tank 1. The recovery pipe 19 is provided with condenser C, for Tiquefying removed unchanged lactde and connected 10 a ‘vacuum pur (n0t shown). Moreover, the horizontal reactor Cis also provided with a heater and a temperature sensor (nese atenct shown). M designates a stirring motor. The horizontal reactor Dis provided witha supply inlet 22, for supplying polymer from the horizontal reactor Cand also provided with a polymer discharge opening 23 Furthermore, like the horizontal reactor C, the horizontal reactor D is provided with sm opening 24 used to reduce pressure inthe tank and connected to a covery pipe 28 for ‘luring removed unchanged lectide to the resetion tank 1 The recovery pipe 25 is provided with a condenser C, for liquefying removed unchanged lactide and connected to a ‘vacuum pump (not shoven). Moreover, the horizontal reactor Cis slo provided with a heater and a temperature sensor (Use are not shown). M designates a stirring motor. By using the above-mentioned coofigutation, polylactic acids are produced as described below. First, E-lactide and eatalyt are supplied to the reaction tank 1from the material supply inlet 2 via the material5,770,682 1 supply pipe 14. AL this time, the valve V is closed. The material supply inlet 2 is thon closed, and a heater (oot shown) andthe full zone impeller 4 are activated to perform polymerization. At this time, polymerization temperature is monitored! and controlled within «predetermined range. § When polymerization progresses and the viscosity of polymer increases afters predetermined time, the valve Vis, ‘opened, and the polymer is supplied from the nozzle into the reaction tank 8. Polymerization continues inthe reaction tank 8 while the spiral bon impeller 12 is aetvated. At this lime, the polymerization temperature is monitored and con- teoled within a predetermined eange. ‘When additional polymerization inthe reaction tank 8 has ‘been completed, the polymer is supplied by the gear pump Prothe horizontal reactor C and vactumed from the opening 18. By the vacuuming, unchanged lacie is introduced into the recovery pipe 19, cooled and liquefied by the eondenser ‘Cys and thea recovered othe reaetion tank I va The opening, 6 When the operation atthe horizoatal reactor C has been ‘completed in a predetermined time, the connection pipe 20, is opened to introduce the polymer inthe borizontal reactor ‘Cinto the borizontal reactor D. The same operation thst performed at he horizontal reactor Cis also performed atthe horizontal reactor D so that unchanged Iactide which was not removed a the horizontal reactor Cis recovered via the ‘opening 7 ‘When the operation at the horizontal reactor D fas been ‘completed the polymer (polyactic acid) is discharged from the opening 23 in the form of a thread, film or stand Inthe above-mentioned operations, the teraperatuces the reaction tanks 1,8 and the horizontal reactor Care set at, 160°C for example, the temperature in the orizonal reactor D isset a 200" for example, and the temperate of the condensers C, and C, are set at 80° to 110° C. for ‘example, In addition, when a phosphioms compound is “added, the aition is performed before presse reduction, namely, atthe preceding stage of the borizonal reactors C {and D by using the connection pipe I provided with an ‘opening for phosphorous eompotin addition Polylactic acid is labile at high temperatures, which rakes it impossible to reduce viscosity by increasing tem perature. In the present invention, lactide ie. the starting ‘monomer itself works as solvent and is reeyeled during the polymerization process to reduce the viscosity of the poly Tactic acid Tn the reaction system where one or mre vertical reactors sre connected in series with one or more horizantal reactors, the polymer product can be smoothly taken out of the ‘vertical reactor, and continuous operations can be achieved ‘Also, since a polymer fre from unchanged lactide can be “obiained by the method ofthe present invention, the © tion step to remove unchanged late from the polymer pret can be omit. EXAMPLES ‘The present invention willbe further described by means of the following working examples, without intending to restrict the seope of the present invention thereto, GPC and DSC in each of Examples were measured under the following conitions: ra Detector: RID-6A, Pump: LC.9A Column oven: CTO.6A, 8 Coluonas: Connecting in series: SHIM PACK GPC-801C, GPC-804C, GPC-806C, and GPC-8025C. Here, the detector, the pump, the columa oven, and the columns are all manufactured by Shimadzu Corporation. ‘Analysis conditions: ‘Solvents Chloroform Flow rate: 1 mlimin Amount of sample: 20 a (lisolving concentration of (05% by weight in chloroform) Column temp. 40° C. psc DSC-50 (manufactured by Shimadzu Corporation) ‘Temperature raising velocity: 10° Cin Amount of sample: 6 t0 7 mg Example 1-1 A homemade lscide of 50 kg was supplied to a 50 1. vertical reactor (reactor A) with full zone impeller (ade ame: Full zoe impeller, manufactured by Shinko Pantec), ‘Alter dissolution at 120° C, 25 g (500 ppm) of tin eeylate Was added and subjected wo reaction at 160° C. for 5 hours. AA this time, unchanged luetide amounted to. 70%. The ‘ements were sent inthe Form of liguid 10 4 50 L. vertical reactor (reactor B) with 2 spiral ribbon impeller (manufactured by Shinko Pantcc), The lactide was futher Subjected to reaction for adlitonal 5 bours, AX this time, tochanged lute amounted to 50%. ‘The contents were introduced ats rate of 10 kghoue into ‘horizontal dualaxis reactor (N-SCR) (reactor C) having an internal eapacity of 65 L (manufactured by Mitsubishi Heavy Irbistries, Lu). The operation temperature of the reactor was set a 164 C., and vacuuming Was performed from a vent (opening) uder 4 reduest pressive of 15, mmonflg. The concentration of the unchanged lncte atthe ‘outlet was 54. The removed latide was liquefied by con- denser having cooling area of 3 mv (manufactured by Karbate), and returned to the reactor A Next the Inte a introduce into am extruder having S barrels (reactor D) made by Kurimoto Lid. and phospho- rous seid Was aed at arate of 10 mg/minut from th tied baerel having been sot at 20 C, Vacutming was performed ‘under a reduced pressure of 15 mmllg from the vent (opening) of the seventh barrel. The removed lsctide was captured by a condenser having a cooling area of 1 m, and returned 10 the reactor A. ‘The polymer was discharged fom 2 spinning oozzle having five holes measuring 01 mm in diameter at a discharging speed of 1.5 winin per hole. The thread thinning ‘completion point was 30-em Grom the spinning nozzle. The polymer shen itrotuced int a cooling pipe. The fiber thus ‘oblained was further subjected fo drawing and heating treatment, and the strength and the tensile elastic modulus of the fiber were evaluated they were 9 qd and 150 gid or more, respectively. The unchanged lactide contained yas about 100 ppm or less, and the molecular weight of the Polymer product vas 150,000, Example 1-2 ‘A homemade lactide of 50 kg was supplied to a 50 1 vertical reactor (feacior A) with a full zone impeller (trade name: Pull zone impeller) After dissolution at 120° C, 05 18 (10 ppm) of tin octylate was added and subjected 0 reaction at 160° C. for S bours. At this time, unchanged luctide amounted to 80 The contents were sent inthe form ‘of liquid to 450 L vertical reactor (eactor B) witha spiral5,770,682 9 ribboa impeller (manufactured by Shinko Paatec). The Ine tide was further subjected to reaction for acitional S ours. AL this time, unchanged lactide amounted to 60%. ‘The contents were introduced ats rate of 10 kyhour io «a borizootal duab-axs reactor (N-SCR) (reactor C) having an internal capacity of 65. (manufactured hy Mitsubishi Heavy Industries, Lu). The operation temperature of the reactor Was set at 160" C., and vacuuming Was perform from a veat (opening) under a reduced pressure of 15 mml¥g. The concentration of the unchanged lactide atthe ‘uilet was 79%, The removed lactide was ligueied by con denser having a cooling area of 3 m* (manufactured by Karbate) and retuned tothe reactor A Next the lactide was inteduced into an extruder baving 8 barrels (eactor D) made by Kurimoto Lid, and vacuum- ing was performed wnder a redvced pressure of 15 mmllg from the ¥eat (¢pening) of the seventh barrel having heen set Aa 200? C. The removed lctde was captured by a condenser having a cooling area of Im, and rete tothe reactor A, The polymer was discharged from a die having thre holes measuring 8 mm in diameter. The polymer is then cooled in ‘water vessel, and cut by a strand cutter to obiain pelle ‘Analysis of the pelletized polymer revealed that weight average molecular weight of the polymer is 155,008 the ‘unchanged lactide contained was about 60 ppm, ass tra- sition temperature was 61° C. Example 1-3 Procedures similar to those in Example 1 were followed ‘except fr the followings. he ate at which the reactant Was, introduced into reactor C was adjusted 10 6.5 kg/hour, ead of 10 kg hour. Also, a gear pump was provided at the ‘ole of the reactor D, abd a spinning nozzle having 48 holes messuring 0.25 mm in diameter was provided down seam the pump, from which the polymer was discharge ‘The polymer wis thea rolled around 4 bobbi ata Hirst and final take-up speed of 800 m/min and 3600 m/min, respectively, at & hotplate temperature of 140° C.to give & seetched thread, The tensile strength of te thread was 45 ‘pd and the elongation a break was 26.2%. Example 2 In a 100{m) flask equipped with a stirrer and theemometer, 5K g of L-lactide was plied. The hetide Was melted at 150? C. while siting ina nitrogen atmosphere, 10 ‘which 0.05 gof tin ootyate was aided. One hot later 0.02 ‘20f phosphoric acid was added to the reaction mixture, the ‘molar ratio of tin compound to phosphoric acid compound being 0.6, and sted for 15 minutes. The contents of the flask was transfered fo a horizontal twin-serew Knesder, in ‘which unchanged late was eemoved at a temperature oF 190F C. under a redueed pressure of 10 mmblg, Ten minutes Tater, pelletized polglactic acid was collected. The molectlar ‘weight of the polylactic acid determined by GPC was 183,000, In a 10-ml test tube, about one g of the polylactic ac ‘obiained above was placed. Tbe internal sir ofthe tes tube ‘was replaced with an N, gas, and the test tube was sealed. Thereafter,» heat decomposition test was carried out by [keeping the fest tube at 190° C. for 30 minutes. The results are shown in Table 2-1 For comparsoa, the same procedures for producing poly- lactic cil a those above were followed without adlition of| phosphoric ack. The polylaetic acid obtained has a motecu- lar Weight of 148,000. This polylactic acid was also sub 10 joted to a heat decomposition lest. The resuls ofthe test are Showa in Table 2-1 ‘As shown in Table 2-1, it was found that polylati acid ‘oblained by the method ofthe present invention has higher Thermal sibility than that obiained by the comparison experiment, Example In a 100ml flask equipped with a stirrer and a thermometer, 500g of L-actide was placed. Te lactde was melted at 140° C. while stirring ina nitrogen atmosphere, to ‘which 0.1 gof tin oetylate was aed, One four liter, 0.2 8 ‘of pyrophosphoric acd was addled to the reaction mixture, the molar ratio of tin compound 10 phosphorus compound boeing 01, and sted for 15 minutes. The contents of the Mask was iansfered to & horizontal twin-setew knee, in ‘which unchanged lactide was removed at a temperature of 1907 C. under reduced pressure of 10 mmHlg. Ten minutes later, pelletized polylatie seid was collected. The molecular ‘weight of the polylaetic acid determined by GPC was 162,000, In a 10-ml est tube, about one g of the polylacic acid ‘oblained above was placed. The interoal aie Of the test tube was replaced with an N_ gas and the test tube was sealed ‘Therealter, a heat decomposition test was carried out by ‘keeping the test tube at 190°C for 30 minutes. The cess ao shown ia Table 2-1, For comparison, the same procedures a those above Were followed without addition of pyrophosphoric acid. The polylactic eid obtained has a molecular weight of 125,00. ‘This polylctc acid was alo subjected to 1 heal decompo= sition test. The resulis ofthe test are shown in Table 2-1 ‘As shown in Table 2-1, it was ound that polylaetie acid ‘blained by the method othe present invention has bight ‘hormal stability than that abiained by the comparison experiment, Example 2-3, In a 1000-ml flask equipped with a stirrer and a thermometer, 500g of L-lactide was placed. The late was melted at 150° C. while stirring in nitrogen atmosphere, 0 which 0.05 gof tin octyate was added. One hour later, 0013 ‘gf phosphoric acid Was added tothe reaction mixture, he molar ratio of tn compound to phosphorus compound being (019, and sted for 15 minutes. The contents of the Mask was, transferred to 2 horizontal twin-screw kneader, in which ‘uachanged Ite Was removed a temperature of 190" C, under a reduced pressure of 10 mllg, Tea minutes later, pelletized polylactic acid was collected, ‘The molecular ‘weight of the polylsetic acid determined by GPC was 168,000. Ina 10-ml est tube, about one g of the polvlacic acid ‘blained above was placed. The interoal air ofthe test tube ‘vas replaced with an N, gas and the test tube was sealed, ‘Thereafter, a heat decomposition test was carried out by ‘keeping the test tube at 190" C. for 30 minutes. Te results are shown in Table 2+, For comparison, the same procedures as thse above were followed without addition of phosphoric acid. The polylactic acid obiained has a molecular weight of 148,000. This polylactc acid was also subjected toa heat decomposition test. The resullsof the fest are shown in Table ‘As shown in Table 2-1, when the molar ratio of tin 49 phosphorus compound exceeds 0.9, the molecular weight of the product s significantly decreased owing to heat decom-5,770,682 uw position and the object of the present invention, therefore, ‘cannot be achieved TABLE 241 Emepena “300 Tan “7 Enele 2 z ple 22 ap op 138 Congeve sin “00 asa mle 23 np sso 2000 pas Compare 88009 ‘sim ah soles Example 3-1 In a 100m! flask equipped with a, stcrer and a thermometer, 1K g of L-lactde was placed. The lactide was. melted at 160° C. while siting ina nitrogen atmosphere, 0 ‘which 0.05 g of in ceiyate was added, Two hours ater, 0.05 13 of aluminum oxide (1.0 time the weight of tin oetyate) ‘was added 10 the reaction mixture, and sted) for 15.2 minutes. The eontenis of the Mask was teansfored to a horizontal swin-serew kneader, in which unchanged lactide ‘yas removed at a temperature of 180° C. under a reduced pressure of 10 malig. Ten minutes later, pelletized poly- lactic acid was collected. The molecular weight of the polylactic acid determined by GPC was 180,000, In-a 10-ml test tube with a stopper, about one g.of the polylactic acid obiained above was placed. The internal air Of the test tube was replaced with an Nz gas. Thereafter, a heat decomposition test was carted out by keeping the test tube at 190" C. for 30 minutes. The resus are shown in “Table 31. Example 3-2 In a 100(-m! flask equipped with a stierer and ‘theemometer, 500g of L-latide was placed. The actide was melted at 1607 C. while siting ina nitogen atmosphere 0 ‘which 0.05 g of tin ceiyate was added. Two hours ater, 0.25 ‘2 of aluminum phosphate (5 times the weight of tin oetyate) was added to the reaction mixture, and sted for 15 minutes. The eontenis of the flask was tansfered to & horizontal twin-serow kneader, ia Which uachinged lactide ‘vas removed at a temperature of 180° C. under 2 reduced pressure of 10) mmlip. Ten minutes later, pelletized poly lactic acid was collected, ‘The molecular weight of the polylactic acid determined by GPC was 185,000, In a 10-ml test tube with a stopper about one of the polylactic acid obtained shove was placed. The internal air ‘ofthe test tube was replaced with an N, gas. Thereafter, heat decomposition test was crsied out by keeping the test tube at 190" C. for 30 minutes. The resus are shown in “Table 31, Example 3-3 In a 1000-m1 flask equipped with a stirer and thermometer, 500 gof L-lactde was placed. The lctide was melted at 1607 C. while siting ina nitrogen atmosphere, 0 ‘hich 0.05 g of tin octyate was added. Two hous later, 0.5 ‘gf ahuminam dihydrogenphosphate (10 times the weight of tin oetyTate) was added to the reaction mixture, and sticed for 15 minutes, The contents ofthe Mask was transferred 10 12 a borizoatal twin-screw kneader, in which unchanged lactide ‘was removed at ¢ fempersture of 180° C. under a reduced pressure of 10 mmlig, Ten minutes later, pelletized poly- lactic acid was collected, The molecular weight of the polslsetic acd determined by GPC was 180,000. Tn a 10eml test tube with « stopper about one g of the polslsetc aid obtained above was placed. The intemal sir Of the test tube was replaced with an Nz gas. Theweafier, 2 beat decomposition test was cartied out by keeping the test tube at 190? . for 30 minutes. The resilis are shown in ‘Table 31 Example 3-4 In 4 1000-m1 flask equipped with a stiver and a ‘thermometer, 500 g of L-lactde was placed, Th Inte was ‘melted at 160° C. while string ina nitrogen atmosphere 0 ‘whieh 0.05 i of tin octylate was added. Two hoes Tater, (0.025 g of aluminum clitydrogenphosphate (05 times the ‘weight of tin ocylate) was added to the reaction mixture, And sired for 15 minutes. The conten of the flask was lransferrd to a borizotal twinescrew Knead, in which changed lactide was removed at a temperature of 180° C under rediced pressuee of 10 mmHlg. Ten minutes late, pelletized polylactic acid was collected. The molecular ‘weight of the polylactic ackl determined by GPC. was 175,000. In a 10-ml test tube with 4 stopper about one of the polslsetie acid obtained above ws placed. The intemal sit Of the test tube was replaced with an N> gas. Thereafter, @ ‘peat decomposition test was cartied out by keeping the test tube at 190" C, for 30 minutes. Tho resis are shown ia Table 31 Example 35 In 4 1000-mi ask equipped with a stirer and thermometer, 500 g of L-lactde was placed, The Inte was ‘melted at 160° C. while string ina nitrogen atmosphere, to ‘whieh 0.05 g of tin octylate was added. Two bours later, 1.0 ‘gof aluminum dinydrogenphosphate (200 times the weight ‘fin oetylate) wes added 10 the reaction mixture, ad sited Tor 15 minutes. The contents ofthe ask was transferred to ‘horizoatal twin-screw kneader, in which unchanged acide was removed at 2 temperature of 180° C. under a educed pressure of 10 mmbig, Ten minutes later, pelletized poly- Tactic acid was collected, The molecular weight of the polslaetie acid determined by GPC was 170,000 Ina 10-ml test tube with & stopper about one g of the polslaetic acid obtained above was placed. The intemal sit of the test tube was replaced with an Nz gas. Thetealier, 2 beat decomposition lest was caried out by keeping the test tube at 190° C. for 30 minutes. The rests are shown io Table 31 Example 36 In 1000.mn1 ask equipped with a stiner and a thermometer, 00 g of L-lactde was placed, The lite was melted at 160°C. while string ina nitrogen atmosphere, to \whiet 0.05 g of in ociglate was acded. Two hours Iser, 0.01, of aluminum ditydrogenphosphate (0.2 times the weight ‘fin oetylate) was added 10 the reaction mixture, ad sited for 15 minutes. The contents ofthe ask was transferred to ‘horizontal twin-screw knetcer, in which unchanged acide ‘was removed at 2 temperature of 180° C. under a reduced pressure of 10 mmbig. Ten minutes later, pelletized! poly Iaetie acid was collected. The molecular weight of the polslactie acid determined by GPC was 160,000$5,770,682 13 Ia a 10-ml est tube with a stopper about one of the polylactic acid obtained above was placed. The internal aie fof the test tube was replaced with an N, gas, Thereafter, & beat decomposition test was earied out by keeping the test tube at 190° C. for 30 minutes. The results are shown in ‘Table 31, Example 37 In a 100{eml flask equipped with a. stcrer and a thermometer, 500 g of L-lactde was placed. The lactide was, ‘melted at 160° C, while stirring in a nittogen almomphiere, 10 ‘which 0.05 g of tin octylate was akled. Two furs ater, 1.2 {oF thiminurn dibydrogenphosphate (24.0 times the weight ‘ftinoetylate) was added 10 the reaction mixture, and sted lor 15 minates. The contents of the Mask was transfered to ‘horizoatal twin-serew kneader, in which unchanged latide ‘was removed at 2 temperature of 180° C. under a educed pressure of 10 mmllg. Ten minutes later, pelletized poly= Iuetic acid was collected. The molecular weight of the polslactc acid determined by GPC was 150,000, * To a 10-ml test tube with a stopper about one g. of the polylactic acd obtained above was placed. The internal aie ff the test tube was replaced with an Nz gas. Thereafter, & heat decomposition test was eartied out by Keeping the test tube at 190° C. For 30 minutes. The resulis are shown in Table 31 ‘Comparative Example 3-1 For comparison, the same procedures 28 the above 2 examples. Were followed without addition of aluminum ‘compound, The poylsctic acid thus obtained had » molecu lar weight of 145,000, This polylactic acid was also sub- {jected to the same heat decomposition test. The results ofthe test are shown in Table 31 As shown in Table 3-1, when polylactic acid was prepared without adding aluminum compound, the mokeeular weight of the product after heat decomposition was significantly lowered, indicating thatthe prot plymer i not thermo stable ‘TABLE 31 ig oe er Icke deception _decmponion mie () tamlese ito 00 Bs Couae soo "en we ample 4-1 In a 100{emi flask equipped with a, stirrer and thermometer, 00 g of L-lactie was placed. The lactide was. ‘melted at 160° C, while stcring in a nitrogen atmosphere, 16 ‘whict 0.05 gof tin octylate was adled. Two firs later, 0.2 'g oT monostearic ack phosphate (40 times the weight of in Setylate) was added tothe raction minture, snd ster for 15 minutes. The contents of the flask was iransforred to a «S| horizontal twin-screw knead, in which unchanged lntide ‘was removed at a temperature of 180° C. under a reduced 14 pressure of 10 mmllg. Ten minutes later, pelletized poly- Tactic acid was collected. The molecular weight of the polylsetie acid determined by GPC was 185,000, In-a 104ml tes! tube with a stopper about one g, of the polylacti acid obtained above was placed, The internal air ff the test tube was seplaced with an N, gas. Tereafir, a heat decomposition lest ws eatied out by keeping the test tube at 190°C, for 30 minutes. The eesills are Showa ia Tile 41 Example 4-2 In & 1000-m1 flask equipped with a stiner and a thermometer, 50 g of L-lactide was placed, The late was relied at 160° C. while siting ina nitrogen atmosphere to ‘which 0.05 g of tin oetylate was add. Two hous later, 0:4 13 of distearic acid phosphate (8.0 times the weight of tin ‘ctylate) was added tothe reaction mixture, and stirred for 415 minutes. The contents ofthe Mask was transferred 0 & horizontal Wwin-serew kneader, in Which unchanged lactide ‘yas removed at a temperature of 180 C. under a reduced ‘pressure of 10 mmllg. Ten minvies later, pelletized poly Tactic acid was collected. The molecular weight of the polylactic acid determined by GPC was 186,000. In a 10-ml tes tube with a stopper about one of the polylatie acid obtained above was placed. The intemal sir ofthe test tube was replaced with an N, gas. Tpereafier, a heat decomposition lest wes catied out by keeping the test tube at 190" C. for 30 minutes. The results are shown ia ‘Table 41 Example 4-3 In 2 1000-1 Mask equipped with a stirer and a thermometer, 50 of L-lactide was place. The lactic was melted at 160°C. while string ina nitrogen aimosphere, to ‘which 0.05 g of tin oetylate was added. Two hours late, 0.7 ‘Bol a mixture of monostearie acid phosphate and dista ‘acid phosphate (Adekastab AX-71) (40 times the weight ‘of tinociylate) was add to the exetion mixture, and sired for 15 minutes. The contents ofthe flask was transferred ves nis) ‘horizontal twin-sew knesder, in which unchanged lactide vas removed ata temperature of 180F C. under a reduced pressure of 10 mmig, Ten minvies later, pelletized poly- Tactic acid was collected, The molecular weight of the polylactic acid determined by GPC was 180,000, Tn a 10-ml tes tbe with a stopper about one 3 of the polylacti acid obtained above was placed, The itera sit of the test tube was replaced with an N, gas. Tpreafier, a5,770,682 15 heat decomposition test was carried out by keeping the test tube at 190° C. for 30 minutes. The results are shown in Table 41, Example 4-4 In a 1000-m1 flask equipped with a, stcrer and a thermometer, 500 gof L-lactde was placed. The let was melted at 160° C. while stirring ina nieogenatmospkere, to which 0.05 g of tin actylate was added. Two hours ler, (0.025 g of Adckastabs AX-71 (03 times the weight of tin ‘ctylate) was added to the reaction mixture, and stirred for 15 minutes. The contents of the flask was transfered to a horizontal twinescrew kneader, in which unchanged lactide ‘was emoved a a temperature of 180° C. under 4 edveed pressure of 10 malig. Ten minutes later, pelletized poly lhctic acid was collected. The molecular weight of the polylacti acid determined by GPC was 172,000. In a 104ml est tube with « stopper about one g of the polylactic acid obtained above was placed. The internal air ‘ofthe test tube was ceplaced with an Nz gas. Theteafer, heat decomposition test was carted cut by keeping the test lube at 190° C. for 30 minutes. The reslls ae shown in Table 41 Example 4-5 In a 1000-m1 flask equipped with a stirrer and ‘thermometer, SI g of L-latide was placed. The lactide was. melted at 1607 C. while string ina nitrogen atmosphere, 10 ‘hich 0.05 g of tin octylate was added, Two hours lier, 0.025 g of Adekasiab AX-71™ (20 times the weight of tin ‘ciylate) was added to the reaction mixture, and stirred for 45 minutes, The contents of the Mask was transferred 10 & horizontal twin-serew kneader, in Which unchanged lactide ‘was removed at a temperature of 180° C. under a reduced pressure of 10 mmf, Ten minutes ater, pelletized poly- lactic acid was collected, The molecular weight of the polylastic acid determined by GPC was 170,000. In a 10-ml fest tbe with a topper about one g of the polylactic acid obtained above was placed. The internal ait ff the test tube was ceplaced with an N- gas. Thereafes, 4 heat decomposition test was curried out by keeping the test tube at 190° C. for 30 minutes. The resis ace shown in Table 41, Example 4-6 In a 100{-m) flask equipped with a stirrer and thesmometer, 50K g of L-latide was placed. The lactide was Ecanple #3 bomple 8 Exanple #7 rome! melted at 160 C. while string ina nitrogen atmosphere 0 16 which 0.05 g of ia octyate was added. Two hours ater, 0.0L 18 of Adekistab AX-TI™ (0.2 times the weight of tin ‘ctylate) was added tothe reaction mixture, and sted for 15 minutes. The contents ofthe flask was transferred to @ ‘horizontal twin-serew Kneader, in which unchanged lactide ‘was removed at 2 temperature of 180° C. under a reduced pressure of 10 mmHg. Ten minutes later, pelletized poly- Tactic acid was collected. ‘The molecular weight of the polylatie acid determined by GPC was 165,000. In-a 10-ml tes tube with a stopper about one g. of the polylactie acid obtained above was place. The internal sir ofthe test tube was replaced with an N, gas. Thereafer, a heat decomposition ext was carted cut by keeping the test, tube at 190°C, for 30 minutes, The resis ate shown in 35 Table 41 Example 47 In a 1000-m1 flask equipped with a stirrer and a thermometer, 500 g of I -lactide was placed. The lactde was relied at 160° C. while stirring ins nian atmosphere, 0 ‘which 005 g of tin ociglate Was added. Two hours later, .2 g of Adekastab AX-7L™ (24 times the weight of in actylate) was aided to the reaction mixture, and stited for 15 minutes. The conten of the Hask was leansfered (0 « horizontal win-serew kncader, in which unchanged lacte wes emoved ata temperature of 180° C. ‘under a reduced pressure of 10 mmbig. Tea minutes later, pelletized polylactie acid was collected, ‘The molecular ‘weight of the polylactic acid determined by GPC was 162,00. Th a 10-ml tex tube with a stopper about one g of the polylactc acid obtained above was placed. The internal ai ‘ofthe test tube was replaced with an N- gas, Thereafer, 4 heat decomposition test was cared ct by keeping the test tube at 100° C. for 30 minutes, The results are shown in ‘Table 41 Comparative Example 4-1 For comparison, the same procedures as the above ‘examples were followed without addition of phosphoric acid ‘ster. The polylstc aid obtained had a molecular weight of 150,000. This polylactic acid was also subjected to the same heat desomposition test. The reslls of the test are shown in Table #1 ‘As shown i Table 4-1, when polylactic acid was prepared ‘without adding phosphoric acid ester, the molecular weight of the product after heat decomposition was significantly lowered, indicating tha the product polymer i not thermo stable TABLE 4-1 ‘Beats _desimostoe deomporton " rae) Cobmice 130000 198 Yew abit)5,770,682 17 Example 5-1 In a 1000-m! flask equipped with a sttrer and ‘thesmometer, 0K g of L-latide was pled. The loctide was relied at 160° C. while siting ina nieogen atmosphere, 10 ‘which 0105 g of tin oetylate was added, One bout late, 0.4 (80 times the weight of fin oetylac) of a mixture of Calcium salt of ethyl bis(3S-diet-butyl-t-hydeoxybenzs! DDhosphorie acid ester and polyethylene wax (I:1, [RGA NOX. 1425 WL) was added to the reaction mixture, and ‘iced for 15 minutes. The contents of the Mask was trans- ferred to a horizontal twin-screw kneader, in which ‘unchanged lactide was removed at a temperature of 180". ‘under 3 reduced presse of 10 mung Ten minutes Iter, pelletized polylactic acid was collected The molecular Weight of the polylsetic acid determined by GPC was 165,000. In a 10-ml test tube with a stopper about one g of the polylactic ac obtained above was placed. The internal ai ‘ofthe test tube was ceplaced with an Nz gas, Thereafes, 4 heat decomposition test was carried out by keeping the test, tube at 190° C. for 30 minutes. The results are shown in “Table 51 Example 5-2 In a 1000-ml flask equipped with a sticrer and 2 thermometer, tM) gof L-Tactide was placed. The let was melted at 1607 C. while stirring ina nicogenatmosplere to which 105 g of tin oetylate was added. One bour later, 0.1 12 of potassium pyrophosphate (2.0 times the weight of tin ‘ciylate) was added to the reaction mixture, and ster for 45 minutes. The contents of the Mask was transferred to 3 horizontal twin-serew Kneader, in which unchanged lactide ‘was removed ata temperate of 180° C. under a reduced pressure of 10 malig. Ten minutes late, pelletized poly Inctic acid was collected. The molecular weight of the polylactic acid determined by GPC was 160,000. In-a 10-ml test tube with a stopper about one g of the polylactic ac obtained above was placed. The internal air ‘of the test tube was ceplaced with an N; gas, Thereafter, 2 heat decomposition test was carried out by keeping the test, tube at 190° C. for 30 minutes. The results ae shown in “Table 51 Example 5-3, In a 100thm! flask equipped with a stirer and ‘theemometer, Sl g of L-lactide was plied. The letide was melted at 1607 C. while stirring ina nitrogen atmosphere, 10 ‘which 0.05 g of tn octylate was added One bour later, 05 ‘2 of sodium dibydrogenphosphate (100 times the weight of lin ceylate) was added to the eaction mixture, and sired for 15 minutes, The contents ofthe Hask was transferred 10 «a borizootaltwin-screw kneade, in which unchanged late ‘was removed at a temperature of 180° C. under a reduced pressure of 10 male, Ten minutes later, pelletized pely- Tactic acid was collected, The molecular weight of the polylactic acid determined by GPC was 170,00. In-a 104ml tes tube with a stopper about one g of the polylictic acid obtained above was placed. The internal aie ofthe test tube was replaced with an N. gas. Thereafer, a heat decomposition test was carried out by keeping the test, tube at 190" C. for 30 minutes, The ress are shown in Table 5-1 Example 5-4 In a 1000-m1 flask equipped with a stirrer and ‘thermometer, SI g of L-latide was placed. The lactide was, 18 relied at 160° C. while stirring ina nitrogen atmosphere, 0 ‘which 0.05 of tin octylate was added. One hour later, 0.025 2 af sodium diydrogenphosphate (0.5 times the weight of tin octylate) was added to the reaction mixture, and sired for 15 minutes. The contens ofthe flask was transfered to ahorigontl tin-screw kneader, in which unebanged lactide ‘was removed at 2 temperature of 180° C. under a reduced pressure of 10 mmHg. Ten minutes later, pelletized poly Tactic acid was collected. The molecular weight of the polylactic acid determined by GPC was 155,000. In a 10-ml test tube with a stopper about one of the polylactic acid obtained abowe was placed. The internal ai ‘of the test tube was replaced with an Nz gas, Theteafer, a heat decomposition test was eased out by keeping the test tube at 100°C for 30 minutes, The results are shown in ‘Table SL Example 5-5 In a 100(hml flask equipped with a stirrer and a thermometer, 5M of I-lactide was placed. The lactde was relied at 160° C. while stirring in niteogen atmosphere, 0 ‘which 0.05 g of tin octylate was added. One hours later, 1.0 go sodium dibydrogenphosphate (20.0 times the weight of Tin octylate) was added tothe reaction mixture, and sired For 15 minutes, The contents ofthe Mask was transferred 10 horizontal twin-screw kneader, in which unchanged lactide was removes! at 3 temperature of 180° C. under a reduced pressure of 10 mills. Ten minates later, pelletized poly- Tactic acid was collected. ‘The molecular weight of the polylatic acid determined by GPC was 155,000. In a 10-ml tes tube with a stopper about one g of the polylactic avid obtained above was placed. The internal sir ‘ofthe test tube was replaced with an Nz gas. Thereafter, a heat decomposition tox! was eared out by keeping the test, lube at 100°C, for 30) minutes, The reslls are shown in Table 5-1, Example 5-6 In a 10001 flask equipped with a stirer and a thermometer, 500 g of L-actide was placed. The Fete 4s relied at 160° C. while stirring ina nitrogen atmosphere, 0 ‘which 0.05 gof tin aeiylate was add. One hour liter, 001 12 of potassium pyrophosphate (02 times the weight Of tin ‘octylate) was added fo the reaction mixture, an stirred for 15 minutes. The contents ofthe flask was transferred to @ horizontal win-serew kneader, in whieh unchanged lactide ‘as removed at a temperature of 180° C. under 2 reduced pressure of 10 mmHg. Ten minutes later, pelletized poly- Tnctic acid was collected. The molecular weight of the polylactie seid determined by GPC was 140,00. In a 10-ml tes tube with a stopper about one g of the polylactc acid obtained above was placed. The internal ir ‘ofthe test tube was replaced with an N> gas, Thereafer, 4 heat decomposition text was arsed cut by keeping the test tube at 190° C. for 30 minutes, The results are shown in ‘Table 5 Example 5-7 In a 1000-ml flask equipped with a stirrer and a thermometer, 500 g of L-Lactide was placed. The lctide was melted at 160° C. while stirring in nitrogen atmosphere, 0 which 0.05 g of tin octylate was added. One bour later, 1.2 12 of potassium pyrophosphate (24 times the weight of tin ‘ctylse) was added tothe reaction mixture, and steed for 15 minutes. The contents of the Mask Was transferred Io a5,770,682 19 horizontal twin-serew kneader, in which unchanged lactide ‘wus removed at a temperature of 180° C. under a reduced pressure of 10 mmf, Ten minutes later, pelletized poly: lactic acid was collected. The molecular weight of the polylactic acid determined by GPC was 150,000. Inu 10-ml test tbe with a stopper about one x, of the polylacti acid obtained above was placed, The internal aie Of the tes tube was ceplaced with an N. gas. Thereafter, 2 heat decomposition test was carried out by keeping the test tube at 190°. for 30 minutes. The results are shown in “Table 51, ‘Comparative Example 5-1 For comparison, the same procedures as the above ‘examples were followed without addition of phosphoric acid metal salt. The polylactic acid oblained had a molecular ‘weight of 145,000. This polylactic acid was also subjected to the same cat decomposition test. The results of the test are shown in Table 5-1 ‘Asshown in Table S-1, when polylsti acid was prepared ‘without adding phosphoric seid este, the molecular weight of the product afer hest decomposition was significantly lowered, indieating thatthe produet polymer isnot thermo: stable ees 2 fe & eee ‘The present invention being thus described, it will be ‘obvious thatthe same may be varied in many ways. Such Variations are not to be regarded as a departure from the Spirit and scope of the invention, and all sich modiieations 18 would be obvious to one skilled inthe art ae intended to be included within the scope of the following claims, What is claimed is 1. A method for producing 8 polylatic acid, comprising the steps of ‘carrying out « ring-opening polymerization of lactide in the presence ofa catalyst for ring-opening polymeriza mn ofthe lactde to give polylactic acid ding a compound capable of inactivating the eatalyst 10 the cesuling reaction mixture; and reducing pressure in a reactor containing the reaction mixture andor allowing an inet gas to passthrough the reactor remove unchanged licide Irom the pose seid 2, The method according to claim 1, wherein the com- pound capable of inactivating the catalyst is added when & ‘weightaverage molecular weight of the polylactic acid produced is 50,000 or moc. 3. The method according to claim 1, wherein the ‘unchanged laetide is removed from the polslactic acid product whic is ina molten or slid state 20 4, The method according to claim 1, wherein the uelianged Tsetide is emoved after the completion of the Fing-opening polymerization. ‘3. The method according to claim 1, wherein the unchanged lactide is removed when amounl of the ‘unchanged lactde becomes 10 to S0% by weight 66. The method sevording to claim 1, wherein the eom: pouod capable of inactivating the catalyst used for ring- ‘opening polymerization is selected from the group consis ing. of (2) phosphoric acid or phosphorous acid, oF the derivatives thereof; and (b) aluioum compounds 7. The method according to claim , wherein the com- pound capable of inactivating the catalyst is added in an mount of 0.5 to 20 times by weight of the amount of a ‘Sitalyst sed for the ring-opening polymerization ‘8. The method according to claim 8, wherein 2 tin ‘compound is used asthe catalyst and a compound selected from (a) of claim 8 is used as the compound capable of inactivating the catalyst for ring-opening, polymerization, the rato of the catalyst to the compound selected from (a) of claim $ being aot ls thao 0.08 and n01 more than 0.9 with 4 proviso that tin is divalent and phosphorus is fetravalen, ‘9. The method according to claim 1, wherein the ‘unchanged lactde removed is recycled 10. The method according 10 claim 1, wherein the ring. ‘opening polymerization of laetide i earred out in a vertical system comprising one or more vertical reactions connected in series and wherein the unchanged lactide is removed ina horizontal system comprising one or more horizontal reac lors connected in series, said vertical system being con- nocted to suid horizontal system in series AL The metbod according to claim 1, wherein the poly- lactic acid fsa copolymer with other monomers. 12. The method according to claim 1, wherein the poly- lactic acid is blended with other resins 13. The method according to claim 8, wherein the unchanged lactide removed in the horizontal system is returned to the vertical system via a recovery line which ‘Snneets the horizontal system with the vertical system s0 a8 to be used as a starting material for the ring-opening polymerization 14. A method for forming fiber or film directly from the polylactic acid produced by the method of claim 1 18, The method of claim I wherein polymerization term- perature i 120° to 180° C. 16, The method of claim I wherein the catalyst is selected from the group consisting of an element of group LA, an clement of Group IVA, an element of group IVB, and an clement of group VB, of the periodic table, and compounds thereof. 17. The method of claim 8, wherein sid tin compound is selected from the group consisting of tin lactate in area,$,770,682 a tin dicaprylate, tin dilaurate, tin dipalmitate, tn distearate, tin dioleste, tin ecnaphihoate, tia Peaaphthoate, and tin ociplate 8. "The method of clsim 6, whervia in said compound ‘capable of inactivating the exalyst is selected feom the ‘0up consisting of pyrophosphorie acd, polyphosphoric cid, monoethyl polyphosphate, diethyl polyphasphate,ti- ethyl phosphate, triphenyl phosphate, telraeiby! pyrophosphate, tetraphenyl pyrophosphate, trimethyl phosphate, methyl phosphite, triethyl phosphite, tripheay] phosphite, hexamethylamide pyrophosphate, adenosine Iriphosphate (ATP), tricalcium phosphate, calcium phosphinate, disodium phosphate, monostearic acid phosphate, distearic acid phosphate, tri-o-butyl phosphate, Iripbenyl phosphite, triphenyl phosphate, diethyl phosphite, 22 clbutyl phosphite, trimethyl phosphite, trbutyl phosphite, dipotassium hydrogenphosphate, potassium clltydrogenphosphate, potassium pyrophesphate, calcium phosphinate, calcium pyrophosphate, disodium hydeogenphesphate, sodium diydeogemphosphat, alumi- ‘ium phosphate, aluminum dibydogenphosphate,bis(35-di- ‘-hutyla-hydroxybenzylphosphorie acid ethyl) calcium, aluminum oxide, alumiaum lactate, aluminum acetylacetonate, aluminum fluoride, aluminum iodide, alu- ‘miaum stearate, aluminum tr-n-butoxid, aluminum tr-s- butoxide, aluminum trethoxide, and aluminum trisopro- poxie,