CN102241816B - Polylactic acid composition containing monosulfonic acid compound and preparation method thereof - Google Patents

Abstract

The invention discloses a polylactic acid composition containing a monosulfonic acid compound and a preparation method thereof. The preparation method of the polylactic acid in the invention comprises the steps of: firstly, dehydrating lactic acid, which is used as raw material, and then subjecting the dehydrated lactic acid to melt polycondensation in the presence of monosulfonic acid and metal compounds to obtain a polylactic acid product; or further subjecting the product derived from the melt polycondensation to solid-phase polymerization reaction to finally obtain the polylactic acid with high molecular weight. In the method, the reaction cycle is shortened by adopting a direct condensation process, thus the polylactic acid with high molecular weight, high thermal stability and high hydrolysis resistance simultaneously can be obtained. The polylactic acid prepared according to the method disclosed by the invention is simple and stable in process, short in polymerization time and relatively low in cost. The invention further discloses a polylactic acid composition containing a sulfonic acid compound and metal compounds, the composition contains the polylactic acid and the sulfonic acid compound as well as contains or does not contain metal compounds except a monosulfonic acid metal compound, wherein the sulfonic acid compound is selected from one or more than one of the monosulfonic acid and the monosulfonic acid metal compounds.

Description

Poly (lactic acid) composition that contains monobasic sulfoacid compound and preparation method thereof

Technical field

The invention belongs to polymeric material field, be specifically related to a kind of method and this poly (lactic acid) composition that utilizes composite catalyst to prepare poly (lactic acid) composition.

Background technology

Poly(lactic acid) (PLA) is relatively a kind of degradable material of many renewable resources origin of research application at present, it be take lactic acid that amylofermentation (or chemosynthesis) obtains as basic raw material prepare a kind of to the nontoxic non-stimulated environment-friendly material of human body, it not only has good physicals, also has good biocompatibility and degradation property.The factor of restriction poly(lactic acid) widespread use mainly contains following two at present: one is that production cost is high, expensive; Another is to compare with general-purpose plastics, and the resistance toheat of poly(lactic acid) and anti-hydrolytic performance are all poor.

Be shown below, at present conventional poly(lactic acid) preparation method mainly can be divided into two kinds of ring-opening polymerization method (indirect method) and direct polycondensation methods (direct method):

(open loop) method is the polymerization route that current most applicability poly(lactic acid) adopts indirectly, first dehydrating condensation between lactic acid molecules is made to lactic acid oligomer, then by oligopolymer degraded, is generated the rac-Lactide of ring-type; Then rac-Lactide ring-opening polymerization is generated to superpolymer.This legal system polylactic acid molecule amount standby and that obtain is higher, better heat stability, and second-order transition temperature and fusing point are all higher.Current maximum poly(lactic acid) manufacturer, the NatureWorks company of the U.S. utilizes ring-opening polymerization to be prepared into the poly(lactic acid) of high molecular, now builds the production equipment of 140,000 tons/year.But (open loop) method production technique is tediously long indirectly, complex process particularly need repeatedly be purified and recrystallization in lactide refined, consumes a large amount of reagent, and high production cost has seriously hindered the widespread use of poly(lactic acid) as a kind of general-purpose plastics material.

In recent years, by the method for acid through direct polycondensation by lactic synthesizing polylactic acid, more and more caused people's concern.Research about Direct Polycondensation of Polylactic Acid has report external morning, and recent year also starts to carry out the research of this respect.Current poly(lactic acid) direct polymerization mainly adopt tin compound as catalyzer or adopt tin compound together with sulfonic acid as composite catalyst.Tin compound is mainly glass putty, tin protoxide, tin protochloride and stannous octoate.Sulfonic acid mainly contains tosic acid and methylsulfonic acid.

Ajioka etc. (Bull Chem Soc Jpn.68,2125,1995) have investigated the katalysis of nearly 20 kinds of metallic elements to the polymerization of lactic acid solution azeotropic, found that to only have the catalytic effect of tin compound more remarkable.Definite says, only has while adopting tin and Bivalent Tin compound (tin protoxide, tin protochloride) and could after long-time polymerization, obtain the poly(lactic acid) of high molecular.But the fusing point lower (163 ℃) of products therefrom, than the low 5-7 ℃ of the fusing point of ring-opening polymerization products therefrom.

Japanese Patent 3436894 (special permission designation) discloses tosic acid and tin protochloride and has been used as composite catalyst while carrying out the polymerization of catalysis lactic acid, can suppress significantly the coloring phenomenon occurring in polymerization process, thereby obtain the polymerisate of excellent quality.Kimura etc. (Polymer, 42,5059,2001) adopt tin protochloride/tosic acid as composite catalyst, have obtained the poly(lactic acid) of high molecular by melting/solid state polymerization technique.

Although adopt tin compound can obtain the poly(lactic acid) of high molecular as composite catalyst as catalyzer or tin compound together with sulfonic acid, but for guaranteeing that polymerization velocity is unlikely to too low, it is long that polymerization time is unlikely to, and generally all has to use larger catalyzer dosage.Such as (Polymer such as Kimura, 42,5059,2001) in report, adopt the stannous chloride dihydrate (with respect to lactic acid polymer) of 0.4wt%, be converted into mol ratio [LA]/[Sn] of lactic acid monomer unit LA and tin atom Sn, [LA]/[Sn]≤778.But being added in when guaranteeing polymerization velocity of a large amount of tin catalysts, has also aggravated side reaction (as racemization, degraded etc.), thereby has caused the fusing point of products therefrom not high, the low and color and luster of thermal stability deteriorated.Although adopt tin protochloride/tosic acid composite catalyst, can improve to a certain extent the color and luster of product and improve to a certain extent the fusing point of product, the poor problem of thermal stability of product is not still resolved.

Summary of the invention

For the problem such as the standby poly(lactic acid) poor heat stability of direct polymerization legal system in prior art, product color and luster be deteriorated, the invention discloses a kind of method of utilizing the composite catalyst synthesizing polylactic acid composition that monobasic sulfonic acid metallizing thing forms together.By present method, preparing poly (lactic acid) composition, to have polymerization velocity fast, and products therefrom has the advantages such as high thermal stability, good color and luster and high-melting-point simultaneously.

On the other hand, for the poor problem of the resistance toheat of poly(lactic acid), the invention provides a kind of poly(lactic acid) and monobasic sulfoacid compound (comprising one or more in monobasic sulfonic acid or monobasic sulfonic acid metallic compound) of containing, contain or do not contain the metallic compound except monobasic sulfonic acid metallic compound; And the poly (lactic acid) composition with advantages such as high thermal stability, good color and luster and high-melting-points.

Object of the present invention can reach by following measures:

The preparation method of poly (lactic acid) composition:

A preparation method for the poly (lactic acid) composition that contains monobasic sulfoacid compound, this preparation method includes take the condensation polymerization operation of the poly (lactic acid) composition that monobasic sulfonic acid and metallic compound prepared as composite catalyst.

Above-mentioned condensation polymerization operation can have two kinds: the first condensation polymerization operation by melt polymerization and solid state polymerization in conjunction with or by melt polymerization, formed separately; Comprise following steps A, comprise or do not comprise following step B:

A) melt polymerization: under inert gas or in the pressure decompression situation that is 0.1～50KPa, take lactic acid, lactic acid oligomer or their composition is raw material, first after processed, add one or more monobasic sulfonic acid and one or more metallic compounds as composite catalyst, at 120～220 ℃, melt phase polycondensation is 4～30 hours, obtains product first;

B) solid state polymerization: by the product first of the steps A after crystallization treatment under inert gas or in the pressure decompression situation that is 0.05～2KPa, be to carry out 8～100 hours solid state polymerizations under the condition of 90～170 ℃ in temperature.

The second condensation polymerization operation is combined into by melt polymerization and solid state polymerization; Comprise following step C and step D:

C) melt polymerization: under inert gas or in the pressure decompression situation that is 0.1～50KPa, take lactic acid, lactic acid oligomer or their composition is raw material, first after processed, add one or more monobasic sulfonic acid as catalyzer 1, at 120～220 ℃ after melt phase polycondensation 2～30h, add again one or more metallic compounds as catalyzer 2, continue at melt phase polycondensation 0～10h at 120～220 ℃, obtain product second;

D) solid state polymerization: by the product second of the step C after crystallization treatment under inert gas or in the pressure decompression situation that is 0.05～2KPa, be to carry out 8～100 hours solid state polymerizations under the condition of 90～170 ℃ in temperature.

Polyester melt polymerization temperature is determined by polymerization single polymerization monomer and gained polyester product, for poly lactic acid polymerized temperature, generally take 80-220 ℃ as good, preferably 120-220 ℃.Melt polymerization temperature is too low, and polymerization velocity is low; Melt polymerization excess Temperature, side reaction aggravation, painted intensification.Polymerization time is mainly depending on target molecular weight, but time oversize product easy coloring generally be take 2-40 hour as good, preferably 4～30 hours.To there is no special requirement adding of catalyzer period, generally after starting with polymerization, in 2 hours, be incorporated as good.The direct polymerization of lactic acid is a reversible reaction with the little equilibrium constant, and the later stage of melt polymerization, the rate of growth of molecular weight increased very slowly or not due to dehydration difficulty, and even the existence due to side reaction causes molecular weight and molecular weight.So be generally difficult to obtain the product of high molecular from melt polymerization.Pass through melt polymerization, the molecular weight of the poly(lactic acid) obtaining is determined by polymerizing condition, generally between several thousand to several ten thousand, adopt to reduce pressure, suitably raise temperature, add strong mixing and extend the molecular weight that the methods such as reaction times can improve the poly(lactic acid) obtaining, in addition in conjunction with the higher catalyst system of catalytic efficiency, the method by melt polymerization also likely obtains molecular weight in more than 100,000 poly(lactic acid).

For poly(lactic acid), after melt polymerization, can adopt the molecular weight of the incompatible further raising poly(lactic acid) of solid polycondensation.By the powder of melt polymerization product or particle after crystallization treatment under inert gas or in the pressure decompression situation that is 0.05～2KPa, solid state polymerization 8～100 hours, wherein pressure was progressively down to 0.05～2KPa from normal pressure in 30～60 minutes.

In melt polymerization process of the present invention, monobasic sulfonic acid metallizing thing can add in system as catalyzer simultaneously, also can first add monobasic sulfonic acid and as polymerization catalyst, after a few hours, add metallic compound again.In the method for rear interpolation metallic compound, can directly finish melt polymerization after adding metallic compound, also can proceed melt polymerization a few hours.Above-mentioned two kinds of catalyzer addition meanss had both been applicable to only carry out the one-step polymerization method of melt polymerization, also be applicable to the two-stage polymerization method that melt polymerization adds solid state polymerization, but in the method for rear interpolation metallic compound, in order to bring into play as far as possible the katalysis of metallic compound, preferably adopt melt polymerization to add the two-stage polymerization method of solid state polymerization.

The present invention has no particular limits the crystallization treatment of melt polymerization product.Can be that the temperature of melt is dropped to isothermal crystal under a certain Tc, also each crystallization some time at series of crystallization temperature; Can be crystallization under air atmosphere, under nitrogen atmosphere, can be also crystallization under vacuum, can also be in water or crystallization in other liquid mediums.Degree of crystallinity of the present invention also has no particular limits.From enrichment degree, inhibition particle or the powder bonded equal angles of end group, consider, degree of crystallinity is more high better.But the too high meeting of degree of crystallinity reduces the activity of end group and reduces polymerization velocity.

The temperature of solid state polymerization determines by second-order transition temperature and the fusing point of poly(lactic acid), that is the temperature of solid state polymerization (Ts) should be between second-order transition temperature (Tg) and fusing point (Tm):

Tg＜Ts＜Tm (1)

Lower than second-order transition temperature, reaction can not be carried out.Higher than fusing point, it is no longer solid state polymerization.Because temperature is low, polymerization velocity is also low.Be generally in the situation that guaranteeing that particle or powder do not melt, should improve polymerization temperature as far as possible.Be greater than under the prerequisite of second-order transition temperature, preferably the temperature range of solid state polymerization be fusing point following 40 ℃ between fusing point:

Tm-40＜Ts＜Tm (2)

Better the temperature range of solid state polymerization be fusing point following 20 ℃ between fusing point:

Tm-20＜Ts＜Tm (3)

The temperature range of best solid state polymerization be fusing point following 10 ℃ between fusing point:

Tm-10＜Ts＜Tm (4)

Because polymerization system molecular weight in polymerization process constantly increases, general degree of crystallinity also can improve constantly, so the fusing point of system also can constantly change in polymerization process.Generally fusing point can improve constantly, and is often to improve comparatively fast at the initial stage, and middle and later periods raising is constant.So in polymerization process, it is constant that the temperature T s of polymerization can keep; Also can constantly change along with polymerisation run; Also can in the early stage Ts be remained on to lower temperature, remain on moderate temperature mid-term and the later stage remains on comparatively high temps; Also can be in the early stage according to polymerisation run, Ts be constantly adjusted and stage is constant at a certain fixed temperature etc.

Due to high molecular polymolecularity, high molecular melting has certain temperature range.So be necessary above-mentioned fusing point (or melt temperature) Tm to be described.Heat-up rate when on the other hand, also being appreciated that polymer fusing point and measuring has certain relation.Tm in the present invention refers to the melt initiation temperature degree of measuring under medium heat-up rate (10～20 ℃/min).

The poly (lactic acid) composition of method prepare to(for) direct condensation of the present invention, the solid phase polymerization temperature scope that it adopts is 70～180 ℃, is 90～170 ℃ preferably.

Direct condensation of the present invention is prepared the monobasic sulfonic acid as catalyzer in the method for poly (lactic acid) composition and can is a kind of monobasic sulfonic acid, also can be the mixture of two or more monobasic sulfonic acid; Same, the metallic compound as catalyzer in the present invention can be a kind of metallic compound, can be also the mixture of two or more metallic compounds.Adding of catalyzer can be that monobasic sulfonic acid metallizing thing adds simultaneously, can be also that monobasic sulfonic acid metallizing thing adds respectively at different time; Further, when the monobasic sulfonic acid as catalyzer is the mixture of two or more monobasic sulfonic acid, different monobasic sulfonic acid can add simultaneously, also can add respectively at different time, equally, when the metallic compound as catalyzer is the mixture of two or more metallic compounds, different metallic compounds can add simultaneously, also can add respectively at different time.

In this preparation method, the type of monobasic sulfonic acid catalyst being had no particular limits, can be aliphatics monobasic sulfonic acid, can be also aromatic series monobasic sulfonic acid.But when poly lactic acid polymerized, aromatic series monobasic sulfonic acid acidity is stronger, easily makes product painted, the anti-hydrolytic performance of product is poor simultaneously, one or more in preferred aliphat monobasic sulfonic acid.Specifically, monobasic sulfonic acid is for having general formula R ' SO ₃a large compounds of H, consider the consistency of itself and poly(lactic acid), wherein R ' is preferably the alkylidene group of C1-C20, the sub-alkynyl group of the alkylene group of the cycloalkylidene of C3-C20, C3-C20, C4-C20, the sub-alkynyl group of replacement of the replacement cycloalkylidene of the substituted alkylene of C1-C20, C3-C20, the replacement alkylene group of C3-C20 or C4-C20.Specifically, R ' can be methylene radical, ethylidene, the propylidene of straight or branched, the butylidene of straight or branched, the pentylidene of straight or branched, the hexylidene of straight or branched, the sub-heptyl of straight or branched, straight or branched octylene, straight or branched nonamethylene, the sub-decyl of straight or branched, the sub-decyl of straight or branched, the sub-undecyl of straight or branched, the sub-dodecyl of straight or branched, the sub-tridecyl of straight or branched, the sub-tetradecyl of straight or branched, the sub-pentadecyl of straight or branched, the sub-hexadecyl of straight or branched, the sub-heptadecyl of straight or branched, the sub-octadecyl of straight or branched, the sub-nonadecyl of straight or branched, or the sub-eicosyl of straight or branched, R ' can be also the substituted alkylene that contains at least one alkyl, cycloalkyl, amino, hydroxyl, alkoxyl group, carboxyl, ester group, acyl group, aldehyde radical, amide group, itrile group, nitro or halogen group, R ' can be also the cycloalkylidene of C3-C20 or the cycloalkylidene of replacement, R ' can be also the alkylene group of the alkylene group of the C3-C20 of ethylene linkage in any position or the C3-C20 of the ethylene linkage of replacement in any position.R ' can also be the sub-alkynyl group of the C4-C20 of acetylene bond in any position or the acetylene bond that the replaces sub-alkynyl group of C4-C20 in any position.R ' is the alkylidene group of C1-C12 more preferably; The more preferably methylsulfonic acid of monobasic sulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, penta sulfonic acid, own sulfonic acid, heptan sulfonic acid, pungent sulfonic acid, the ninth of the ten Heavenly Stems sulfonic acid, the last of the ten Heavenly stems sulfonic acid, 1-undecane sulfonic acid, 1-dodecane sulfonic acid or 1-eicosane sulfonic acid.R ' is further preferably the alkylidene group of C1-C6.Monobasic sulfonic acid be further preferably methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, penta sulfonic acid or own sulfonic acid.

Total add-on as the monobasic sulfonic acid of catalyzer in the preparation method of poly (lactic acid) composition of the present invention is pressed sulfonate radical-SO ₃in H, the quality of element sulphur is counted the 0ppm-20000ppm (not comprising 0) of lactic acid or lactic acid units quality, consider the mechanical property of product, thermostability, balance between hydrolytic resistance and catalytic performance, be preferably 10-8000ppm, be preferably again 100ppm-5000ppm, 200ppm-4000ppm more preferably, that best is 300-3000ppm.

In the preparation method of poly (lactic acid) composition of the present invention, as the metallic element in the metallic compound of catalyzer, be selected from one or more in IA-IVA Zu, IB-VIIB Zu, VIII family's metallic element or thulium; Consider catalytic activity, be preferably Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Sm, Eu, Er, Yb, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Al, Ge, Sn, Pb, Sb, one or more in Bi; Consider the thermostability of product, be preferably one or more in Ti, Mn, Fe, Cu, Zn, Al, Ge, Pb, Sb or Ce, Ti more preferably, Zn, one or more in Sb or Ce, most preferably are Ti, one or more in Zn or Sb.Metallic compound can be one or more in the mineral compound of the monomer of above-mentioned metal, the organic compound of above-mentioned metal or above-mentioned metal.Specifically, metallic compound can be the monomer of above-mentioned metal, halogenide, oxide compound, oxyhydroxide, carbonate, vitriol, nitrate, phosphoric acid salt, silicate, borate, oxymuriate, chromic salt, manganate, arsenate, cyanate, alkyl carboxylate, alkyl dicarboxylic aid's salt, alkyl multi-carboxylate, substituted alkyl carboxylate salt, substituted alkyl dicarboxylate, substituted alkyl multi-carboxylate, aromatic base carboxylate salt, aromatic base dicarboxylate, aromatic base multi-carboxylate, substituted aromatic base carboxylate salt, substituted aromatic base dicarboxylate, substituted aromatic base multi-carboxylate, alkylsulfonate, substituted alkyl sulfonate, aromatic sulfonate, substituted aromatic base sulfonate, acetylacetonate, one or more in alkyl alkoxide or substituted alkyl alkoxide, metallic compound be preferably one or more in monomer, halogenide, oxide compound, vitriol, borate, alkyl carboxylate, substituted alkyl carboxylate salt, alkyl dicarboxylic aid's salt, substituted alkyl dicarboxylate, alkyl multi-carboxylate, substituted alkyl multi-carboxylate, alkylsulfonate, substituted alkyl sulfonate, aromatic sulfonate, substituted aromatic base sulfonate, acetylacetonate, alkyl alkoxide or the substituted alkyl alkoxide of above-mentioned metal, one or more in the monomer of the more preferably above-mentioned metal of metallic compound, muriate, oxide compound, vitriol, fluoroborate, acetate, oxalate, octylate, Citrate trianion, metilsulfate, ethyl sulfonate, propyl sulfonic acid salt, butyl sulfosalt, amyl group sulfonate, acetylacetonate or alkyl alkoxide.

Total add-on as the metallic compound of catalyzer in the preparation method of poly (lactic acid) composition of the present invention is counted the 0-200000ppm (not comprising 0) of lactic acid or lactic acid units quality with metallic element quality, consider the mechanical property of product and the balance between catalytic performance, be preferably 0-100000ppm, more preferably 10-80000ppm, is preferably 10-30000ppm.In the preparation method of poly (lactic acid) composition of the present invention, the ratio of monobasic sulfonic acid metallizing thing add-on is not had to special requirement, consider thermostability and the hydrolytic resistance of product, the ratio of monobasic sulfonic acid metallizing thing add-on be take in monobasic sulfonic acid in element sulphur metallizing thing the mol ratio of metallic element as 0.1/1～300/1 for well, be 0.5/1～100/1 preferably, be better 0.5/1～60/1, best is 0.5/1～40/1.The ratio of monobasic sulfonic acid metallizing thing add-on is too small, may affect the thermostability of catalytic performance and poly(lactic acid), the too high anti-hydrolytic performance that may affect poly(lactic acid).

In the method for preparing poly (lactic acid) composition of the present invention, lactic acid monomer can not done any processing before polymerization; Also can be before polycondensation to the raw material pre-treatment of dewatering.Certainly, the dehydration here not only refers to physics dehydration, also may relate to condensation dehydration simultaneously.In this treating processes, no matter whether there is the existence of extra catalyst, condensation (polycondensation) may inevitably occur.

In not damaging the scope of the object of the invention, can in this polymerization process, add various auxiliary agents, as: antioxidant, photostabilizer, painted inhibitor etc.

As the antioxidant using in the present invention, can enumerate sterically hindered phenol based compound, bi-ester of phosphite, sulfide compound etc.As the example of sterically hindered phenol based compound, can enumerate Octadecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, Octadecane base-3-(3 '-methyl-5 '-tertiary butyl-4 '-hydroxy phenyl) propionic ester, n-tetradecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, 1,6-hexylene glycol-bis--[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], BDO-bis--[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,2 '-methylene-bis-(4-methyl-tert-butyl phenol), triethylene glycol-bis--[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)-propionic ester], four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-methylethyl] 2,4,8,10-tetra-oxaspiros (5,5) undecane, N, N '-bis--3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionyl hexamethylene-diamine, N, N '-tetramethylene-bis--3-(3 '-methyl-5 '-tertiary butyl-4 '-hydroxyl phenol) propionyl diamines, N, N '-bis--[3-(3,5-di-t-butyl-4-hydroxyl phenol) propionyl] hydrazine, N-salicylyl-N '-salicylidene hydrazine, 3-(N-salicylyl) amino-1,2,4-triazole, N, N '-bis-[2-{3-(3,5-di-tert-butyl-hydroxy phenyl) propionyloxy } ethyl] oxyamide etc.Preferably: triethylene glycol-bis--[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)-propionic ester] and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane.

As phosphorous acid ester based compound, preferably at least 1 P-O bond is incorporated into the compound on aromatic series base, as concrete example, can enumerate three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyls) 4,4 '-Ya biphenyl phosphinate, two (2,4-di-tert-butyl-phenyl) tetramethylolmethane-bis--phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-bis--phosphorous acid ester, 2,2-methylene-bis (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 4,4 '-butylidene-bis-(3-methyl-6-tert butyl phenyl-bis--tridecyl) phosphorous acid ester, 1,1,3-tri-(the 2-methyl-4-double tridecyl phosphorous acid ester-5-tertiary butyl-phenyl) butane, three (mixing single and two-nonyl phenyl) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, 4, the different base of 4 '-Ya two (phenyl-dialkyl phosphites) etc., what can preferably use is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, two (4,6-di-tert-butyl-phenyl) the octyl group phosphorous acid esters of the sub-different base of 2,2-, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-bis--phosphorous acid ester, four (2,4-di-tert-butyl-phenyls) 4,4 '-biphenylene phosphorous acid ester etc.

Concrete example as thioether based compound, can enumerate dilauryl thiodipropionate, two-tridecyl thiodipropionate, myristyl thiodipropionate, two octadecyl thiodipropionate, tetramethylolmethane-tetra-(3-lauryl thiopropionate), tetramethylolmethane-tetra-(3-dodecyl thiopropionate), tetramethylolmethane-tetra-(3-octadecyl thiopropionate), tetramethylolmethane-tetra-(3-myristyl thiopropionate), tetramethylolmethane-tetra-(the hard ester acyl of 3-thiopropionate) etc.

As the photostabilizer using in the present invention, can enumerate benzophenone based compound, benzotriazole based compound, aromatic series benzoic ether based compound, oxalic acid aniline based compound, cyanoacrylate based compound and bulky amine based compound etc.Concrete example as benzophenone based compound, can enumerate, benzophenone, 2, 4-dihydro benzophenone, 2, 2 ', 4, 4 '-tetrahydro-benzophenone, ESCALOL 567, 2, 2 '-dihydroxyl-4, 4 '-dimethoxy-benzophenone, 2, 2 '-dihydroxy benaophenonel, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4 dodecyl benzophenone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone, 5-chlorine-2-hydroxyl benzophenone, 2, 2 '-dihydroxyl-4, 4 '-dimethoxy-5-diphenylsulfone ketone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2-hydroxyl-4-(2-hydroxy-3-methyl-acryloxy isopropoxy benzophenone etc.

Concrete example as benzotriazole based compound, can enumerate, 2-(2 '-hydroxyl-5 '-methyl-phenyl)-benzotriazole, 2-(2-hydroxyl-3, 5-bis--uncle-amyl group phenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-3, 5 '-bis--tertiary butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis--tertiary butyl-5 '-methyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis--tertiary butyl-phenyl) the chloro-benzotriazole of-5-, 2-(2 '-hydroxyl-3 ', 5 '-bis--uncle-isopentyl-phenyl) benzotriazole, (2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-bis-(α, α-dimethylbenzyl) phenyl] benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-bis-(α, α-dimethylbenzyl) phenyl]-2H-benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole etc.

As the concrete example of aromatic series phenylformic acid based compound, can enumerate the alkyl phenyl salicylate classes such as p-tert-butyl-phenyl salicylate, p-octyl phenyl salicylate.

As the concrete example of oxalic acid amino benzenes compounds, can enumerate 2-oxyethyl group-2 '-ethyl oxalic acid dianiline, the 2-oxyethyl group-5-tertiary butyl-2 '-ethyl oxalic acid dianiline, 2-oxyethyl group-3 '-dodecyl oxalic acid dianiline etc.

As the concrete example of cyanoacrylate based compound, can enumerate ethyl-2-cyano group-3,3 '-phenylbenzene-acrylate, 2-ethylhexyl-2-cyano group-3,3 '-phenylbenzene-acrylate etc.

As the concrete example of bulky amine based compound, can enumerate 4-acetoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine, 4-acryloxy-2,2,6,6-tetramethyl piperidine, 4-(phenylacetyl oxygen base)-2,2,6,6-tetramethyl piperidine, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, 4-methoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine, 4-cyclohexyloxy-2,2,6,6-tetramethyl piperidine, 4-benzyloxy-2,2,6,6-tetramethyl piperidine, 4-phenoxy group-2,2,6,6-tetramethyl piperidine, 4-(ethylamino methanoyl)-2,2,6,6-tetramethyl piperidine, 4-(cyclohexyl carboxyamide oxygen base)-2,2,6,6-tetramethyl piperidine, 4-(phenyl amino methanoyl)-2,2,6,6-tetramethyl piperidine, two (2,2,6,6-tetramethyl--4-piperidyl)-carbonic ether, two (2,2,6,6-tetramethyl--4-piperidyl)-barkite, two (2,2,6,6-tetramethyl--4-piperidyl)-malonic ester, two (2,2,6,6-tetramethyl--4-piperidyl)-sebate, two (2,2,6,6-tetramethyl--4-piperidyl)-adipic acid ester, two (2,2,6,6-tetramethyl--4-piperidyl)-terephthalate, two (2,2,6,6-tetramethyl--4-piperidyl oxygen)-ethane of 1,2-, α, α '-bis-(2,2,6,6-tetramethyl--4-piperidyl oxygen)-p-dimethylbenzene, two (2,2,6,6-tetramethyl--4-piperidyl cresylene-2,4-diurethaness, two (2,2,6,6-tetramethyl--4-piperidyl)-hexa-methylene-1,6-diurethanes, three (2,2,6,6-tetramethyl--4-piperidyl)-benzene-1,3,5-tricarboxylic ester, three (2,2,6,6-tetramethyl--4-piperidyl)-benzene-1,3,4-tricarboxylic ester, 1-[2-{3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionyloxy }-butyl]-4-[3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionyloxy } 2,2,6,6-tetramethyl piperidine, 1,2,3,4-BTCA and 1,2,2,6,6-pentamethyl--4-piperidine alcohols and β, β, β ', β '-tetramethyl--3,9-[2,4,8,10-, tetra-oxaspiros (5,5) undecane] condenses etc. of ethylene glycol.

Poly (lactic acid) composition:

A kind of poly (lactic acid) composition that contains monobasic sulfoacid compound being obtained by above-mentioned preparation method, said composition contains poly(lactic acid) and monobasic sulfoacid compound, contains or do not contain monobasic sulfonic acid metallic compound metallic compound in addition; Wherein said monobasic sulfoacid compound is selected from one or more in monobasic sulfonic acid, monobasic sulfonic acid metallic compound.

In this composition, monobasic sulfonic acid metallic compound can, by directly obtaining to adding monobasic sulfonic acid metallic compound in composition, also can add respectively monobasic sulfonic acid and metallic compound and to composition and in composition, form monobasic sulfonic acid metallic compound.Composition in the present invention can be for containing the composition of poly(lactic acid), monobasic sulfonic acid, monobasic sulfonic acid metallic compound and the metallic compound except monobasic sulfonic acid metallic compound, also can be for containing the composition of poly(lactic acid), monobasic sulfonic acid, monobasic sulfonic acid metallic compound, also can be for containing the composition of poly(lactic acid), monobasic sulfonic acid metallic compound and the metallic compound except monobasic sulfonic acid metallic compound, can also be for containing the composition of poly(lactic acid) and monobasic sulfonic acid metallic compound.

This composition has no particular limits the type of monobasic sulfoacid compound, can be aromatic series monobasic sulfoacid compound, can be also aliphatics monobasic sulfoacid compound, can also be the combination of aromatic series monobasic sulfoacid compound and aliphatics monobasic sulfoacid compound.Consider color and luster and the anti-hydrolytic performance of poly (lactic acid) composition, in this composition, monobasic sulfonic acid is preferably one or more in aliphatics monobasic sulfonic acid; Monobasic sulfonic acid metallic compound is preferably one or more in aliphatics monobasic sulfonic acid metallic compound.Specifically, monobasic sulfoacid compound for have general formula (R " SO ₃) _ax _ba large compounds, a wherein, b is the integer that is greater than zero, R " be hydrocarbon chain or the replacement hydrocarbon chain of C1-C30, X can be H element; can be also one or more in IA-IVA Zu, IB-VIIB Zu, VIII family's metallic element or thulium; in fact, when X is H element, this monobasic sulfoacid compound is monobasic sulfonic acid; when X is metallic element, and this monobasic sulfoacid compound is monobasic sulfonic acid metallic compound.Consider the consistency of itself and poly(lactic acid), R wherein " be preferably the alkylidene group of C1-C20, the sub-alkynyl group of the alkylene group of the cycloalkylidene of C3-C20, C3-C20, C4-C20, the sub-alkynyl group of replacement of the replacement cycloalkylidene of the substituted alkylene of C1-C20, C3-C20, the replacement alkylene group of C3-C20 or C4-C20.Specifically, R " can be methylene radical, ethylidene, the propylidene of straight or branched, the butylidene of straight or branched, the pentylidene of straight or branched, the hexylidene of straight or branched, the sub-heptyl of straight or branched, straight or branched octylene, straight or branched nonamethylene, the sub-decyl of straight or branched, the sub-decyl of straight or branched, the sub-undecyl of straight or branched, the sub-dodecyl of straight or branched, the sub-tridecyl of straight or branched, the sub-tetradecyl of straight or branched, the sub-pentadecyl of straight or branched, the sub-hexadecyl of straight or branched, the sub-heptadecyl of straight or branched, the sub-octadecyl of straight or branched, the sub-nonadecyl of straight or branched, or the sub-eicosyl of straight or branched, R " can be also the substituted alkylene that contains at least one alkyl, cycloalkyl, amino, hydroxyl, alkoxyl group, carboxyl, ester group, acyl group, aldehyde radical, amide group, itrile group, nitro or halogen group, R " can be also the cycloalkylidene of C3-C20 or the cycloalkylidene of replacement, R " can be also the alkylene group of the alkylene group of the C3-C20 of ethylene linkage in any position or the C3-C20 of the ethylene linkage of replacement in any position.R " can also be the sub-alkynyl group of the C4-C20 of acetylene bond in any position or the acetylene bond that the replaces sub-alkynyl group of C4-C20 in any position.R " alkylidene group of C1-C12 more preferably; The more preferably methylsulfonic acid compound of monobasic sulfoacid compound, ethyl sulfonic acid compound, propanesulfonic acid compound, fourth sulfoacid compound, penta sulfoacid compound, own sulfoacid compound, heptan sulfoacid compound, pungent sulfoacid compound, the ninth of the ten Heavenly Stems sulfoacid compound, the last of the ten Heavenly stems sulfoacid compound, 1-undecane sulfoacid compound, 1-dodecane sulfonic acid compound or 1-eicosane sulfoacid compound.R " be further preferably the alkylidene group of C1-C6.Monobasic sulfoacid compound be further preferably methylsulfonic acid compound, ethyl sulfonic acid compound, propanesulfonic acid compound, fourth sulfoacid compound, penta sulfoacid compound or own sulfoacid compound.

In this composition, the total content of sulfoacid compound is pressed group-SO ₃the quality of-middle element sulphur is counted 0ppm-30000ppm (not comprising 0), consider the mechanical property of product, thermostability, balance between hydrolytic resistance and catalytic performance, be preferably 10-12000ppm, be preferably again 140ppm-7500ppm, 280ppm-5800ppm more preferably, that best is 400-4500ppm.

Metallic element in this composition in metallic compound is selected from one or more in IA-IVA Zu, IB-VIIB Zu, VIII family's metallic element or thulium; Consider catalytic activity, be preferably Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Sm, Eu, Er, Yb, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Al, Ge, Sn, Pb, Sb, one or more in Bi; Consider the thermostability of product, be preferably one or more in Ti, Mn, Fe, Cu, Zn, Al, Ge, Pb, Sb or Ce, Ti more preferably, Zn, one or more in Sb or Ce, most preferably are Ti, one or more in Zn or Sb.Metallic compound can be one or more in the mineral compound of the monomer of above-mentioned metal, the organic compound of above-mentioned metal or above-mentioned metal.Specifically, metallic compound can be the monomer of above-mentioned metal, halogenide, oxide compound, oxyhydroxide, carbonate, vitriol, nitrate, phosphoric acid salt, silicate, borate, oxymuriate, chromic salt, manganate, arsenate, cyanate, alkyl carboxylate, alkyl dicarboxylic aid's salt, alkyl multi-carboxylate, substituted alkyl carboxylate salt, substituted alkyl dicarboxylate, substituted alkyl multi-carboxylate, aromatic base carboxylate salt, aromatic base dicarboxylate, aromatic base multi-carboxylate, substituted aromatic base carboxylate salt, substituted aromatic base dicarboxylate, substituted aromatic base multi-carboxylate, alkylsulfonate, substituted alkyl sulfonate, aromatic sulfonate, substituted aromatic base sulfonate, acetylacetonate, alkyl alkoxide, or one or more in substituted alkyl alkoxide, metallic compound be preferably one or more in monomer, halogenide, oxide compound, vitriol, borate, alkyl carboxylate, substituted alkyl carboxylate salt, alkyl dicarboxylic aid's salt, substituted alkyl dicarboxylate, alkyl multi-carboxylate, substituted alkyl multi-carboxylate, alkylsulfonate, substituted alkyl sulfonate, aromatic sulfonate, substituted aromatic base sulfonate, acetylacetonate, alkyl alkoxide or the substituted alkyl alkoxide of above-mentioned metal, one or more in the monomer of the more preferably above-mentioned metal of metallic compound, muriate, oxide compound, vitriol, fluoroborate, acetate, oxalate, octylate, Citrate trianion, metilsulfate, ethyl sulfonate, propyl sulfonic acid salt, butyl sulfosalt, amyl group sulfonate, acetylacetonate or alkyl alkoxide.

In this composition, the total content of metallic compound is in metallic element quality 0-300000ppm (not comprising 0), consider the mechanical property of product and the balance between catalytic performance, be preferably 0-150000ppm, more preferably 10-120000ppm, is preferably 10-45000ppm.In this composition, the ratio of monobasic sulfoacid compound metallizing thing is not had to special requirement, consider thermostability and the hydrolytic resistance of composition, the ratio of monobasic sulfoacid compound metallizing thing be take in monobasic sulfoacid compound in element sulphur metallizing thing the mol ratio of metallic element as 0.1/1～300/1 for well, be 0.5/1～100/1 preferably, be better 0.5/1～60/1, best is 0.5/1～40/1.The ratio of monobasic sulfoacid compound metallizing thing is too small, may affect the thermostability of poly (lactic acid) composition, the too high anti-hydrolytic performance that may affect poly (lactic acid) composition.

Poly (lactic acid) composition of the present invention has higher thermostability, also has good anti-hydrolytic performance simultaneously.

In poly (lactic acid) composition of the present invention, in the scope of not damaging object of the present invention, can contain various auxiliary agents, as: antioxidant, photostabilizer, painted inhibitor etc.Above-mentioned auxiliary agent kind is described in poly (lactic acid) composition preparation method.

In poly (lactic acid) composition of the present invention, in the scope of not damaging object of the present invention, can also contain nucleator, weather resisting agent, lubricant, releasing agent, fire retardant, dyestuff, antistatic agent, whipping agent etc.

The composite catalyst forming with monobasic sulfonic acid metallizing thing provided by the invention is prepared the method for poly-lactic acid in high molecular weight composition at short notice by the direct condensation of lactic acid, make method that direct condensation prepares poly(lactic acid) in the industrial possibility that becomes.With respect to tin compound, separately as catalyzer, composite catalyst of the present invention has higher polymerization activity, can make products therefrom thermostability significantly improve simultaneously; With respect to monobasic sulfonic acid, separately as catalyzer, composite catalyst of the present invention has higher polymerization activity, can make products therefrom hydrolytic resistance significantly improve simultaneously, and color and luster is greatly improved; With respect to monobasic sulfonic acid/tin compound composite catalyst, adopt monobasic sulfonic acid/metallic compound composite catalyst provided by the invention to be aggregated in when guaranteeing polymerization activity and can make products therefrom thermostability significantly improve.The present invention has the advantage of aforementioned three kinds of methods concurrently and without corresponding shortcoming, the range of application of poly(lactic acid) and the performance of the finished product is all greatly improved.The method can obtain there is high molecular simultaneously, high thermal stability, hydrolytic resistance and colory poly(lactic acid).By the present invention, prepare poly(lactic acid), its technique simple and stable, polymerization time is short, cost is relatively cheap and product is pure etc.The poly (lactic acid) composition that contains sulfoacid compound and metallic compound of the present invention by the synergy between sulfoacid compound metallizing thing, makes composition have that thermostability is high, anti-hydrolytic performance good, colory advantage simultaneously.

Embodiment

Below in conjunction with embodiment, the invention will be further described, but this does not illustrate that the present invention only limits to these embodiment.

For being described as follows of the raw material the present invention relates to:

Pfansteihl: Jiangxi Musashi wildlife Chemical Co., Ltd., the 90wt% aqueous solution.

Sulfonic acid and metal catalyst: buy from Sigma-Aldrich Aladdin, Alfa easer, the reagent companies such as traditional Chinese medicines

For being described as follows of the test the present invention relates to:

Weight-average molecular weight (Mw), the Japanese Shimadzu LCsolution GPC of company, 30 ℃, chromatographic grade trichloromethane leacheate, PS standard.

Fusing point (Tm), the DSC Q-100 of U.S. TA company.Sample after 2 minutes, at the speed borehole cooling to 0 ℃ of 20 ℃/min, then is warmed up to 200 ℃ 200 ℃ of meltings from 0 ℃ of speed with 20 ℃/min.Tm determines by this heating curve, and its value is the thermal spike of melting peak.

Thermal destruction speed (thermal weight loss speed), U.S. TA company's T GA-Q100.Under 100ml/min nitrogen gas stream, isothermal records at 200 ℃.

Hydrolysis, the GL-04KA of Guangzhou Espec Environmental Equipment Co., Ltd type climatic chamber, 60 ℃, under 90% relative humidity, process 5 days, with GPC, measure the weight-average molecular weight of hydrolysis front and back poly(lactic acid), by the molecular weight of front and back, calculated the range of decrease of weight-average molecular weight.

Embodiment 1:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, add 10161mg aluminum oxide (it is 29874ppm with respect to lactic acid quality that add-on be take metallic element, lower with), (add-on is with sulfonate radical-SO for methylsulfonic acid 4325mg ₃in H, element sulphur quality meter is 8000ppm with respect to lactic acid quality, lower same).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 68%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:15.8 ten thousand.Fusing point Tm:165 ℃.Melt color and luster: micro-Huang.Thermal destruction speed: 1.01wt%/min.The molecular weight range of decrease after hydrolysis: 22%.

Embodiment 2:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds two propyloic three oxidation two germanium (O[Ge (=O) CH ₂cH ₂cOOH] ₂) 14.72mg (35ppm), ethyl sulfonic acid 2835mg (4576ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 72%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:16.5 ten thousand.Fusing point Tm:168 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.031wt%/min.The molecular weight range of decrease after hydrolysis: 30%.

Embodiment 3:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds tetrabutyl titanate 541mg (423ppm), 1-propanesulfonic acid 933mg (1336ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 18 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 69%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:20.2 ten thousand.Fusing point Tm:170 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.092wt%/min.The molecular weight range of decrease after hydrolysis: 15%.

Embodiment 4:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds two hydration three manganese acetates (15654ppm), the 1-propanesulfonic acid 3527mg (5050ppm) of 13748mg.Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 68%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:21.9 ten thousand.Fusing point Tm:168 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.45wt%/min.The molecular weight range of decrease after hydrolysis: 15%.

Embodiment 5:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds ferric acetyl acetonade 458mg (402ppm) and 1-fourth sulfonic acid 1038mg (1336ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 18 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:16.1 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.081wt%/min.The molecular weight range of decrease after hydrolysis: 19%.

Embodiment 6:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds copper powder 153mg (851ppm), lead nitrate 245mg (851ppm), 1-sulfonic acid in last of the ten Heavenly stems 1679mg (1336ppm) and 1-propanesulfonic acid 933mg (1336ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.1KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 69%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:17.4 ten thousand.Fusing point Tm:168 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.085wt%/min.The molecular weight range of decrease after hydrolysis: 18%.

Embodiment 7:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure to 2-ethylenehydrinsulfonic acid 948mg (1336ppm) under nitrogen protection.Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), add four hydration citrate of lime 2211mg (863ppm) and continue reaction and pour out after 0.5 hour, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.1KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:16.4 ten thousand.Fusing point Tm:168 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.097wt%/min.The molecular weight range of decrease after hydrolysis: 20%.

Embodiment 8:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds diamino sulfonic acid nickel 335mg (435ppm) and 1-eicosane sulfonic acid 2734mg (1336ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 69%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:13.2 ten thousand.Fusing point Tm:167 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.093wt%/min.The molecular weight range of decrease after hydrolysis: 19%.

Embodiment 9:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds zinc chloride 21mg (55ppm) and 1-propanesulfonic acid 1866mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 71%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:17.2 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.003wt%/min.The molecular weight range of decrease after hydrolysis: 22%.

Embodiment 10:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds antimony acetate 5.3mg (12ppm) and 1-propanesulfonic acid 7.68mg (11ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:6.7 ten thousand.Fusing point Tm:165 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.101wt%/min.The molecular weight range of decrease after hydrolysis: 9%.

Embodiment 11:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds titanium isopropylate 465mg (435ppm) and 1-propanesulfonic acid 933mg (1336ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 68%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:19.5 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.09wt%/min.The molecular weight range of decrease after hydrolysis: 18%.

Embodiment 12:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds four cerium sulfate hydrate 229mg (441ppm) and 2-naphthene sulfonic acid 626mg (534ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 69%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:17.4 ten thousand.Fusing point Tm:168 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.02wt%/min.The molecular weight range of decrease after hydrolysis: 42%.

Embodiment 13:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds ethyl sulfonic acid 1655mg (2672ppm) and antimonous oxide 462mg (2143ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.1KPa and pressure is remained on to melt polymerization 0.1KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 68%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:20.6 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.099wt%/min.The molecular weight range of decrease after hydrolysis: 18%.

Embodiment 14:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds zinc oxide 100mg (448ppm) and ethyl sulfonic acid 1655mg (2672ppm).At 120,140,160,180,200 and 220 ℃, (corresponding pressure is at each temperature 50KPa, 10KPa, 5KPa, 0.3KPa, 0.2KPa and 0.1KPa in turn) each melt polymerization was poured out and is obtained poly(lactic acid) product after 5 hours (amounting to 30 hours) subsequently.Weigh to such an extent that the observed yield Y% of whole polymerization process is 66%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:15.5 ten thousand.Fusing point Tm:168 ℃.Melt color and luster: micro-Huang.Thermal destruction speed: 0.02wt%/min.The molecular weight range of decrease after hydrolysis: 12%.

Embodiment 15:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds Magnesium Stearate 1874mg (428ppm) and ethyl sulfonic acid 1655mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 1KPa.Pear shape bottle is immersed in silicone oil bath and oil bath temperature is raised to 90 ℃, 100 ℃, 110 ℃ and keeping at each temperature 1 hour in turn.(corresponding pressure is at each temperature 2KPa, 1KPa, 0.5KPa, 0.3KPa, 0.2KPa, 0.2KPa, 0.1KPa and 0.05KPa in turn) each solid state polymerization 12 hours at 130,140,150,155,160,162,164 and 166 ℃, amounts to solid state polymerization 96 hours subsequently.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 69%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:22.3 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.04wt%/min.The molecular weight range of decrease after hydrolysis: 16%.

Embodiment 16:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds zinc chloride 656mg (1744ppm) and ethyl sulfonic acid 1655mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:28.5 ten thousand.Fusing point Tm:170 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.05wt%/min.The molecular weight range of decrease after hydrolysis: 8%.

Embodiment 17:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds zinc chloride 65.6mg (174ppm) and ethyl sulfonic acid 1655mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 71%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:20.1 ten thousand.Fusing point Tm:170 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.005wt%/min.The molecular weight range of decrease after hydrolysis: 15%.

Embodiment 18:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds ethyl sulfonic acid 1655mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), add antimony acetate 60.7mg (174ppm) and continue melt polymerization under these conditions and pour out after 10 hours, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:18.8 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.01wt%/min.The molecular weight range of decrease after hydrolysis: 23%.

Embodiment 19:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and under the nitrogen gas stream of 100L/h, dewater 2.5 hours.Add ethyl sulfonic acid 828mg (1336ppm), by system temperature rise to 160 ℃ and under 160 ℃ and nitrogen gas stream melt polymerization after 6 hours, add antimonous oxide 149mg (428ppm) and continue under these conditions melt polymerization 0.25 hour, pour out, the cooling poly(lactic acid) prepolymer that obtains.10g prepolycondensate particle (particle diameter 1-3mm) is put into stainless-steel pipe (internal diameter 2cm, long 10cm), from steel pipe bottom, pass into the nitrogen gas stream (100L/h) having heated.After being put into oil bath and oil bath temperature is raised to 110 ℃, steel pipe and nitrogen pipeline (long 3m) keep 2 hours.Be warming up to subsequently 168 ℃ of solid state polymerizations 20 hours.Take out particle and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:20.0 ten thousand.Fusing point Tm:170 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.05wt%/min.The molecular weight range of decrease after hydrolysis: 14%.

Embodiment 20:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds methylsulfonic acid 1445mg (2672ppm) and stannous acetate 113mg (316ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:21.1 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 1.38wt%/min.The molecular weight range of decrease after hydrolysis: 19%.

Embodiment 21:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds zinc chloride 656mg (1744ppm) and tosic acid 2588mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 70%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:29.1 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.03wt%/min.The molecular weight range of decrease after hydrolysis: 39%.

Comparative example 1:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds stannous acetate 113mg (316ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 68%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:11.7 ten thousand.Fusing point Tm:169 ℃.Melt color and luster: colourless.Thermal destruction speed: 2.45wt%/min.The molecular weight range of decrease after hydrolysis: 16%.

Comparative example 2:

In 500mL four-hole boiling flask, inject after the Pfansteihl aqueous solution 200g of 90wt%, flask is put into oil bath.On four-hole boiling flask, install agitator, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 ℃ and dewater.From dehydration, start system pressure in 60 minutes and progressively from normal pressure, be reduced to 5KPa; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); Now, with nitrogen, system pressure is returned to after normal pressure, under nitrogen protection, adds methylsulfonic acid 1445mg (2672ppm).Then system temperature rises to 160 ℃, pressure was progressively reduced to 0.3KPa and pressure is remained on to melt polymerization 0.3KPa condition from normal pressure in 2 hours and after 4 hours (amounting to 6 hours), pour out, the cooling poly(lactic acid) prepolymer that obtains.The prepolycondensate powder 100g that is 100-250um by particle diameter puts into the 1L pear shape bottle of Rotary Evaporators and uses afterwards nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.Pear shape bottle is immersed after being raised to 110 ℃ in silicone oil bath and by oil bath temperature and kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain poly(lactic acid) product.Weigh to such an extent that the observed yield Y% of whole polymerization process is 69%.By product sample is tested, obtain following salient features:

Weight-average molecular weight Mw:6.4 ten thousand.Fusing point Tm:163 ℃.Melt color and luster: colourless.Thermal destruction speed: 0.02wt%/min.The molecular weight range of decrease after hydrolysis: 23%.

Embodiment effect comparison:

Part embodiment effect is listed in table 1.In embodiment 2, the add-on mol ratio of ethyl sulfonic acid and two propyloic three oxidation two germanium is [S]/[Ge]=296, is higher value, and after hydrolysis, the range of decrease of weight-average molecular weight is 30%, the better heat stability of product, and its thermal destruction speed is 0.031wt%/min.In embodiment 9, the add-on mol ratio of 1-propanesulfonic acid and zinc chloride is [S]/[Zn]=99, compared with embodiment 2, reduces to some extent, and the anti-hydrolytic performance of product makes moderate progress, and after hydrolysis, the weight-average molecular weight range of decrease is 22%, and the thermal destruction speed of product is 0.003wt%/min.In embodiment 16, the add-on mol ratio of ethyl sulfonic acid and zinc chloride is [S]/[Zn]=3, for less value, the excellent hydrolysis resistance of product, after hydrolysis, the range of decrease of weight-average molecular weight is 8%, due to the increase of zinc chloride add-on, the thermostability of product declines to some extent compared with embodiment 9, and its thermal destruction speed is 0.05wt%/min.In embodiment 17, the add-on mol ratio of ethyl sulfonic acid and zinc chloride is [S]/[Zn]=31, compared with embodiment 16, increases to some extent, the anti-hydrolytic performance of product declines to some extent, after hydrolysis, the range of decrease of weight-average molecular weight is 15%, and the thermostability of product increases, and its thermal destruction speed is 0.005wt%/min.In embodiment 20, methylsulfonic acid and stannous acetate add-on mol ratio are [S]/[Sn]=31, identical with embodiment 17, but because metal compound as catalyst is stannous acetate, therefore it is poor that the thermostability of product is compared embodiment 17, its thermal destruction speed is 1.38wt%/min, but hydrolytic resistance variation is little, and after hydrolysis, the weight-average molecular weight range of decrease is 19%.In embodiment 21, the add-on mol ratio of tosic acid and zinc chloride is [S]/[Zn]=3, identical with embodiment 16, but because the monobasic sulfonic acid catalyst adopting is tosic acid, therefore it is poor that the anti-hydrolytic performance of product is compared embodiment 16, after hydrolysis, the weight-average molecular weight range of decrease is 39%, but product thermostability and embodiment 16 be more or less the same, and its thermal destruction speed is 0.03wt%/min.In comparative example 1, employing be stannous acetate separately as catalyzer, its catalytic efficiency is limited, the molecular weight of product is only 11.7 ten thousand, simultaneously the thermostability of product is very poor, its thermal destruction speed is up to 2.45wt%/min.In comparative example 2, employing be methylsulfonic acid separately as catalyzer, its catalytic efficiency is lower, the molecular weight of product is only 6.4 ten thousand.In sum, in order to reach the thermostability of catalytic performance, product and the balance between hydrolytic resistance three, preferred catalyzer is aliphatics monobasic sulfonic acid and the metallic compound composite catalyst except tin compound, and in its add-on, the most preferred range of the mol ratio of element sulphur and metallic element is between 0.5/1～40/1.

Table 1 embodiment and comparative example effect comparison table

Embodiment

Embodiment 2:

Embodiment 9:

Embodiment 16:

Embodiment 17:

Embodiment 20:

Embodiment 21:

Comparative example 1:

Comparative example 2:

Polyester monocase and quality

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

90wt%L-lactic acid 200g

Monobasic sulfonic acid and quality

Ethyl sulfonic acid 2835mg

1-propanesulfonic acid 1866mg

Ethyl sulfonic acid 1655mg

Ethyl sulfonic acid 1655mg

Methylsulfonic acid 1445mg

Tosic acid 2588mg

Nothing

Methylsulfonic acid 1445mg

Monobasic sulfonic acid add-on C s0/ppm

4576

2672

2672

2672

2672

2672

-

2672

Metallic compound and quality

Two propyloic three oxidation two germanium 14.72mg

Zinc chloride 20.64mg

Zinc chloride 656mg

Zinc chloride 65.6mg

Stannous acetate 113mg

Zinc chloride 656mg

Stannous acetate 565mg

Nothing

Metallic compound add-on C m0/ppm

35

55

1744

174

316

1744

1582

-

Monobasic sulfonic acid metallizing thing add-on mol ratio [S]/[Metal]

296

99

3

31

31

3

-

-

Melt polymerization conditions

160℃*0.3KPa*6h

160℃*0.3KPa *6h

160℃*0.3KP a*6h

160℃*0.3KP a*6h

160℃*0.3K Pa*6h

160℃*0.3 KPa*6h

160℃*0.3KP a*6h

160℃*0.3KP a*6h

Solid phase polymerization conditions

158℃*0.2KPa *24h

158℃*0.2KPa *24h

158℃*0.2KP a*24h

158℃*0.2KP a*24h

158℃*0.2K Pa*24h

158℃*0.2 KPa*24h

158℃*0.2KP a*24h

158℃*0.2KP a*24h

Observed yield Y%

72％

71％

70％

71％

70％

70％

65％

69％

Weight-average molecular weight/ten thousand

16.5

17.2

28.5

20.1

21.1

29.1

11.7

6.4

Melt color and luster

Colourless

Colourless

Colourless

Colourless

Colourless

Colourless

Colourless

Colourless

Thermal destruction speed wt%/min

0.031

0.003

0.05

0.005

1.38

0.03

2.45

0.02

The weight-average molecular weight range of decrease after hydrolysis

30％

22％

8％

15％

19％

39％

10％

21％

Claims (8)

1. the preparation method of a poly (lactic acid) composition that contains monobasic sulfoacid compound, it is characterized in that: this preparation method includes take monobasic sulfonic acid and metallic compound and prepare the condensation polymerization operation of poly (lactic acid) composition as composite catalyst, wherein metallic compound is selected from Ti, Mn, Fe, Cu, Zn, Al, Ge, Pb, the monomer of Sb or Ce, muriate, oxide compound, vitriol, fluoroborate, acetate, oxalate, octylate, Citrate trianion, metilsulfate, ethyl sulfonate, propyl sulfonic acid salt, butyl sulfosalt, amyl group sulfonate, one or more in acetylacetonate or alkyl alkoxide, described monobasic sulfonic acid is selected from one or more in aliphatics monobasic sulfonic acid.

2. the preparation method of poly (lactic acid) composition according to claim 1, is characterized in that: described condensation polymerization operation comprises following steps A, comprises or do not comprise following step B:

A) melt polymerization: under inert gas or in the pressure decompression situation that is 0.1～50KPa, take lactic acid, lactic acid oligomer or their composition is raw material, first after processed, add one or more monobasic sulfonic acid and one or more metallic compounds as composite catalyst, at 120～220 ℃, melt phase polycondensation is 4～30 hours, obtains product first;

B) solid state polymerization: by the product first of the steps A after crystallization treatment under inert gas or in the pressure decompression situation that is 0.05～2KPa, be to carry out 8～100 hours solid state polymerizations under the condition of 90～170 ℃ in temperature.

3. the preparation method of poly (lactic acid) composition according to claim 1, is characterized in that: described condensation polymerization operation comprises following step C and step D:

C) melt polymerization: under inert gas or in the pressure decompression situation that is 0.1～50KPa, take lactic acid, lactic acid oligomer or their composition is raw material, first after processed, add one or more monobasic sulfonic acid as catalyzer 1, at 120～220 ℃ after melt phase polycondensation 2～30h, add again one or more metallic compounds as catalyzer 2, continue at melt phase polycondensation 0～10h at 120～220 ℃, obtain product second;

D) solid state polymerization: by the product second of the step C after crystallization treatment under inert gas or in the pressure decompression situation that is 0.05～2KPa, be to carry out 8～100 hours solid state polymerizations under the condition of 90～170 ℃ in temperature.

4. according to the preparation method of the poly (lactic acid) composition described in any one in claim 1～3, it is characterized in that: total add-on of described monobasic sulfonic acid is with sulfonate radical-SO ₃in H, the quality of element sulphur is counted the 10ppm-8000ppm of lactic acid or lactic acid units quality.

5. according to the preparation method of the poly (lactic acid) composition described in claim 1, it is characterized in that: the metallic element in described metallic compound is selected from one or more in Ti, Zn, Sb or Ce.

6. according to the preparation method of the poly (lactic acid) composition described in any one in claim 1～3, it is characterized in that: total add-on of described metallic compound is counted the 10ppm-30000ppm of lactic acid or lactic acid units quality with metallic element quality.

7. the poly (lactic acid) composition that contains monobasic sulfoacid compound that prepared by method claimed in claim 1, is characterized in that: said composition contains poly(lactic acid) and monobasic sulfoacid compound, contains or do not contain monobasic sulfonic acid metallic compound metallic compound in addition; Wherein monobasic sulfoacid compound is selected from one or more in monobasic sulfonic acid, monobasic sulfonic acid metallic compound; Wherein metallic compound is selected from one or more in monomer, muriate, oxide compound, vitriol, fluoroborate, acetate, oxalate, octylate, Citrate trianion, metilsulfate, ethyl sulfonate, propyl sulfonic acid salt, butyl sulfosalt, amyl group sulfonate, acetylacetonate or the alkyl alkoxide of Ti, Mn, Fe, Cu, Zn, Al, Ge, Pb, Sb or Ce; Described monobasic sulfonic acid is selected from one or more in aliphatics monobasic sulfonic acid.

8. according to the poly (lactic acid) composition described in claim 7, it is characterized in that: described metallic compound is selected from one or more in Ti, Zn, Sb or Ce compound.